Wavelength converting pixel films, and display devices including the same

Abstract

Described herein is a wavelength converting pixel film composition and / or a film containing the same that has improved quantum efficiency and color gamut. The wavelength converting pixel film composition and / or film includes a film media, a blue light absorbing compound, and at least one photoluminescent dye, the photoluminescent dye including a blue absorbing moiety, and a photoluminescent dye.

Description

[0001] WAVELENGTH CONVERTING PIXEL FILMS, AND DISPLAY DEVICES INCLUDING THE SAME

[0002] Inventors: Jie Cai, Shijun Zheng, and 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] Photoluminescent substances are materials that emit light after absorbing energy forms such as 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.

[0007] Recently, a variety of attempts to modify the spectrum of a light source using photoluminescent substances have been described. Photoluminescent substances absorb specific wavelengths of light from a light source, convert it to light of a longer wavelength in a visible region, and emit the light of the longer wavelength. 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 activator ions and a parent compound such as a sulfide, an oxide or a nitride, 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 expensive, have low light emission efficiency, and the emission of light in a near ultraviolet or blue region of 400 nm or higher is limited.

[0008] Quantum dot technology has achieved a high level of quantum efficiency and color gamut. However, cadmium-based quantum dots may be 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.

[0009] Therefore, there is a need for additional contributions in this area of technology. SUMMARY

[0010] The present disclosure relates to wavelength converting pixel films and lightemitting display devices including the same.

[0011] In one embodiment, a wavelength converting media or wavelength converting pixel film may include a film media, a blue light absorbing compound and at least one photoluminescent dye. The blue light absorbing compound and the photoluminescent dye are disposed within the film media. In some forms, the wavelength converting media or wavelength converting pixel film may include a green pixel including a first photoluminescent dye. In some forms, the wavelength converting media or wavelength converting pixel film may further include a red pixel including a second photoluminescent dye. In some forms, the first photoluminescent dye may include a green narrowly emitting moiety. In some forms, the green narrowly emitting moiety may emit a green wavelength light with an emission spectrum having a full width half maximum of less than about 40 nm. In some embodiments, the green narrowly emitting moiety may have a peak emission at about 510 nanometers to about 540 nanometers. In some forms, the second photoluminescent dye may include a red narrowly emitting moiety. In some forms, the red narrowly emitting moiety may emit a red wavelength light with an emission spectrum having a full width half maximum of less than about 50 nm. In some forms, the red narrowly emitting moiety may have a peak emission at about 600 nm to about 660 nm.

[0012] In some forms, the wavelength converting media or wavelength converting pixel film may further include scattering centers. In some forms, the scattering centers may be disposed within the film media. In some forms, the film media may include a transparent substrate or a translucent substrate.

[0013] In some forms, the first photoluminescent dye may include a FRET (Forster Resonance Energy Transfer) green dye. In some forms, the FRET green dye may include a blue light absorbing compound. In some forms, the second photoluminescent dye may include a FRET green dye and a non-FRET red dye. In some forms, the second photoluminescent dye may include a non-FRET green dye and a non-FRET red dye.

[0014] In some forms, the blue light absorbing compound may be a compound according to the following general formula: , wherein: R1is one of an aryl, a substituted aryl (such as a C1-C5alkyl substituted aryl) and a C1-C8alkyl; and each of R2, R3, R4, R5and R6is independently selected from H and an aryl substituted with at least one trihaloalkyl. In some forms, at least one of R2, R3, R4, R5and R6is an aryl substituted with at least one trihaloalkyl. In some forms, R1may be where each of R7and R8is a C1-C5alky. In some forms, R1may be In some forms, R2R3,R4, R5 and R6 may independently be one of H, In some forms, the blue light absorbing compound may have one of the following structures:

[0015]

[0016] In some forms, the first photoluminescent dye may have one of the following structures:

[0017] In some forms, the second photoluminescent dye may have one of the following structures:

[0018]

[0019]

[0020] In some forms, the wavelength converting media or wavelength converting pixel film may have an internal quantum yield of greater than about 80%, and an external quantum yield of greater than about 40%. In some forms, the wavelength converting media or wavelength converting pixel film may have a thickness of less than about 10 pm.

[0021] In one embodiment, a printed layer includes a wavelength converting media or wavelength converting pixel film described herein. In some forms, the printed layer may absorb blue light and convert the blue light to green or red light with a sharp emission spectral, which may be used as a color pixel layer for a display application. In some forms, the printed layer may further include a transparent substrate and the wavelength converting media or wavelength converting pixel film further includes a plurality of scattering centers. In some forms, the printed layer may further include plural dots of the wavelength converting media or wavelength converting pixel film described herein. In some forms, the plural dots may be located over predetermined pixel locations of a light emitting device. In some forms, the plural dots may be sized to cover the predetermined pixel locations of the light emitting device.

[0022] In one embodiment, a light emitting device includes the wavelength converting media or wavelength converting pixel film described herein. In some embodiments, a backlit device is described having a blue light source, and the backlit device includes the wavelength converting media or wavelength converting pixel film described herein.

[0023] These and other embodiments are described in greater detail below.

[0024] BRIEF DESCRIPTION OF THE DRAWINGS

[0025] FIG. 1 is a schematic illustration of an embodiment of a display device including a WLC film described herein.

[0026] FIG. 2 is a schematic illustration of an embodiment of a display device including a WLC film described herein.

[0027] DETAILED DESCRIPTION

[0028] The present disclosure relates to wavelength converting media, such as a wavelength converting pixel film, including photoluminescent compounds (or dyes) having a high quantum efficiency and high color gamut output.

[0029] The term “BODIPY” as used herein refers to a chemical moiety according to the following formula:

[0030] The BODIPY moiety may include a dipyrromethene complexed with a disubstituted boron atom (BX2), typically a BF2 or a B(CN)2 unit. The IUPAC name for the BODIPY core (i.e. , without any substituents, and without the aryl group opposite the BX2 group, wherein X=F) is 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene. In some forms, R1, R2, R3, R4, R5, R6may independently be one of H, a C1-3alkyl, aryl, ether, ester, and a phenyl group. In some forms, R7 and R8 may independently be one of H, a methyl group (-CH3), an aryl group, an isopropyl group and Cl. In some forms, R7and R8may be The BODIPY moiety of the present disclosure may be a BODIPY moiety wherein R3and R4may independently be an aryl, e.g., a phenyl group; and R1, R2, R5, and / or R6may independently be one of H, substituted aryl, e.g., an optionally substituted phenyl group The term “isoquinoline” or “isoquinoline derivative” or “xanthenoisoquinoline derivative” as used herein, refers to a chemical moiety according to the following formula: where X = NR and R may be a linking group or an aryl group, and Y may be a hydrogen group, a C1-C3alkyl, or an aryl group, e.g., a benzyl group. The term “naphthalimide” or “naphthalimide derivative” as used herein, refers to a chemical moiety according to the following formula: , wherein: R1is one of an aryl, a substituted aryl (such as a C1-C5alkyl substituted aryl) and a C1-C8alkyl; and each of R2, R3, R4, R5and R6is independently selected from H and an aryl substituted with at least one trihaloalkyl. In some forms, at least one of R2, R3, R4, R5and R6is an aryl substituted with at least one trihaloalkyl. In some forms, the BODIPY moiety may be a separate compound within the film composition, e.g., a blue light or wavelength absorbing compound. In some forms, the BODIPY moiety is connected to an isoquinoline moiety with a linking group, e.g., a photoluminescent dye, and the photoluminescent dye may include a blue light or wavelength absorbing moiety and a narrowly emitting moiety such as, a narrowly green light emitting moiety or a narrowly red-light emitting moiety. In one embodiment, a pixel film includes a solvent or dispersing medium, a blue light absorbing compound and / or moiety, and an organic photoluminescent compound. In some forms, the first blue light absorbing compound and / or moiety may be separate or apart from (e.g., not covalently bound to) a filming group and / or a narrowly emitting green or red-light moiety. In some forms, the pixel film may include both a first organic photoluminescent dye and a second organic photoluminescent dye. In some forms, the pixel film may include a first organic photoluminescent dye that is green-emitting and have an emissive peak with a full width half maximum of less than about 40 nm. In some forms, the pixel film composition may include an alternative and / or a second organic photoluminescent dye that is red-emitting and has an emissive peak with a full width half maximum of less than about 50 nm. In some forms, the film may include light scattering centers. In some forms, the blue absorbing moiety, green emitting organic photoluminescent dye (emitting green light) and / or the red emitting organic photoluminescent dye (emitting red light), and / or the scattering centers may be disposed within the pixel film such as within a film suspending or dispersing media and / or polymer matrix. In some forms, the pixel film composition or materials containing the same may provide a high quantum yield. In some forms, the pixel film composition or materials containing the same may provide a quantum yield between about 80% to about 95%. In some forms, an LCD backlight may include the aforementioned film. In some forms, the pixel film composition may include a polymer matrix. When present, the polymer matrix may have a transparency of greater than about 75%, although other variations are contemplated. In some forms, the polymer matrix may include a hydrophilic polymer. In some more particular but non-limiting forms, the polymer matrix may include polyvinyl butyral, polyvinyl acetate, polyvinyl alcohol, or a polyacrylate. The polymer matrix may additionally or alternatively include ethyl cellulose and / or polyester or copolymers including the same. In one non-limiting form, the polyacrylate may be a polyalkylacrylate such as polymethylmethacrylate (PMMA). The solvent of the film composition and / or the film containing the same may be a non-polar solvent, e.g., an organic solvent, and / or a polar solvent. In some forms, the film composition and / or the film containing same may be dispersed, dissolved and / or mixed with a solvent. By way of example, in some forms the solvents may be used in the manufacture of material layers. For examples, the solvents may be used to disperse or solubilize the blue absorbing moiety, fluorescent moieties, etc., for use in printer cartridges or for disposition on a desired substrate, or in the manufacture of material layers Non-limiting examples of non-polar solvents which may be used include, but are not limited to, xylenes, cyclohexanone, acetone, toluene, methyl ethyl ketone, or any combination thereof. Non-limiting examples of polar solvents which may be used include ethanol, dimethylformamide (DMF), or a combination thereof. In some forms, the solvent may be a combination of non-polar and polar solvents. A non-limiting example of a solvent based pixel film may be an ultra-mild solvent clear film containing 2-ethoxy ethyl ether (product number SB.UMS.3000, STS films, Boca Raton, FLA, USA). In one or more forms, a pixel film may generally include a total of about 0.5% to about 15% by weight, or more particularly about 1.5% to about 8% by weight, (reckoned dry) of one or more of the compounds described herein. Microemulsion films are based on organic solvents and water with or without an additional hydrotropic substance (interface mediator). Microemulsion films may include about 0.5% to about 15% by weight, or about 1.5% to about 8% by weight, of one or more of the compounds described herein, about 5% to about 99% by weight of water, and about 0.5% to 94.5% by weight of an organic solvent and / or a hydrotropic compound, although other variations in these amounts and ranges are possible and contemplated. Solvent based pixel films may include about 0.5% to 15% by weight of one or more compounds described herein, and about 85% to about 99.5% by weight of an organic solvent and / or a hydrotropic compound, although other variations in these amounts and ranges are possible and contemplated. Hot-melt films are based mostly on waxes, fatty acids, fatty alcohols or sulfonamides that are solid at room temperature and liquefy on heating, with a melting range lying between about 60 °C and about 140 °C. Hot-melt pixel films may include for example about 20% to about 90% by weight of wax and about 1 to about 10% by weight of one or more of the compounds described herein. In some forms, the hot-melt pixel films may be limited, or generally limited, to these materials. However, other variations are possible. For example, the hot-melt films may further include about 0% to about 20% by weight of an additional polymer (e.g., as a dye solvent), about 0% to about 5% by weight of a dispersant, about 0% to about 20% by weight of a viscosity modifier, about 0% to about 20% by weight of a plasticizer, about 0% to about 10% by weight of a tack additive, about 0% to about 10% by weight of a transparency stabilizer (which prevents crystallization of waxes for example), and about 0% to about 2% by weight of an antioxidant. Additional details regarding additives and assistants which may be included in a hot-melt film are provided for example in U.S. Pat. No.5,560,760. In some forms, a photoluminescent compound (and / or the photoluminescent wavelength converting film including the photoluminescent compound) may have 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). As used herein, FWHM defines the width, in nanometers, of the absorption or emission spectrum at half the absorption or emission peak wavelength. In some forms, the photoluminescent compound may have an absorption band with a FWHM value that is less than or equal to about 50 nm, less than or equal to about 40 nm, less than or equal to about 35 nm, less than or equal to about 30 nm, or less than or equal to about 25 nm when dispersed in a substantially transparent polymer matrix. In some forms, the photoluminescent compound may have an emission band with a FWHM value that is less than or equal to about 50 nm, less than or equal to about 40 nm, less than or equal to about 35 nm, or less than or equal to about 30 nm when dispersed in a substantially transparent polymer matrix. In one or more forms, the blue light absorbing compound may include a naphthalic imide group, or it may include an isoquinoline alkyl derivative. In some forms, the blue light absorbing compound may be a derivate selected from the photoluminescent dyes described in co-pending U.S. Provisional Application No. 63 / 152,309, which is incorporated herein by reference for its discussion of photoluminescent dyes and to U.S. Provisional Application No. 63 / 278,904, Attorney Docket No. N3253.10133US02, and U.S. Provisional Application No. 63 / 379,633, Attorney Docket No. N3253.10153US02, which are incorporated herein by reference. In some forms, the blue light absorbing compound may be a compound according to the following general formula: , wherein: R1is one of an aryl, a substituted aryl (such as a C1-C5alkyl substituted aryl) and a C1-C8alkyl; and each of R2, R3, R4, R5and R6is independently selected from H and an aryl substituted with at least one trihaloalkyl. In some forms, at least one of R2, R3, R4, R5and R6is an aryl substituted with at least one trihaloalkyl. In some forms, R1may be where each of R7and R8is a C1-C5alky. In some forms, R1may be In some forms, R2R3,R4, R5and R6may independently be one of H, and . In some forms, the blue light absorbing compound may have one of the following structures:

[0031] In one or more forms, the blue light absorbing compound may be similar to or the same as the blue absorbing moiety of the green and / or red emitting compounds described herein. In some forms, the blue light absorbing compound may be a derivative of a different blue absorbing moiety of the green and / or red emitting compounds described herein. In one embodiment, a pixel film may include an organic photoluminescent dye (which may include a BODIPY group), a filming group, and an isoquinoline group. By way of non-limiting example, the isoquinoline group may be an isoquinoline derivative group or a xanthenoisoquinoline derivative group. In some forms, the BODIPY group when included in the organic photoluminescent dye may be covalently bonded to the filming group. Additionally or alternatively, the filming group may be covalently bonded to the isoquinoline group, or to the isoquinoline derivative group or the xanthenoisoquinoline derivative group. In one embodiment, a pixel film composition and / or film containing the same may include a first organic photoluminescent compound (or dye). In one form of this embodiment, the pixel film composition and / or film containing the same may further include a second organic photoluminescent compound (or dye). In one embodiment, a wavelength converting media may include a green pixel including a first photoluminescent dye. In one form of this embodiment, the wavelength converting media may also include a red pixel including a second photoluminescent dye. In some forms, the first organic photoluminescent dye may include a green narrowly emitting moiety, and the green narrowly emitting moiety may emit a green wavelength light with an emission spectrum having a full width half maximum of less than about 40 nm. Further, in some forms, the second organic photoluminescent dye may include a red narrowly emitting moiety and the red narrowly emitting moiety may emit a wavelength light with an emission spectrum having a full width half maximum of less than about 50 nm. In some forms, the first photoluminescent dye may include a FRET (Forster Resonance Energy Transfer) green dye. In some forms, the FRET green dye may include a blue light absorbing compound. In some forms, the second photoluminescent dye may include a FRET green dye and a non-FRET red dye. In other forms, the second photoluminescent dye may include a non-FRET green dye and a non-FRET red dye.

[0032] In one or more forms, the first organic photoluminescent dye (and / or a photoluminescent wavelength converting film including the organic photoluminescent dye) may have an emission peak between about 510 nm and about 540 nm. In some forms, the emission peak may be between about 500-515 nm, about 515-520 nm, about 520-525 nm, about 525-530 nm, about 530-535 nm, about 535-540 nm, about 540-545 nm, about 545-550 nm, about 550-555 nm, about 555-560 nm, or about 510 nm, about 520 nm, about 530 nm, about 540 nm, or any wavelength in a range bounded by any these values (green light emitting). In some form, the emissive spectrum of the first organic photoluminescent dye and / or of a photoluminescent wavelength converting film including the same may have a full width half maximum (FWHM) of less than about 50 nm, less than about 45 nm, less than about 40 nm, less than about 35 nm, less than about 30 nm, less than about 25 nm, or less than about 20 nm.

[0033] In some forms, the first organic photoluminescent dye may be a photoluminescent dye described in co-pending U.S. Provisional Application No. 63 / 152,309, which is incorporated herein by reference for its discussion of photoluminescent dyes, and U.S. Provisional Application No. 63 / 278,904, Attorney Docket No. N3253.10133US02, which is incorporated herein by reference.

[0034] In one or more forms, the first organic photoluminescent dye may include one or more of the following compounds:

[0035]

[0036]

[0037] As indicated above, in some forms a photoluminescent wavelength converting film or a film including the same may include a second organic photoluminescent dye. By way of example, the second organic photoluminescent dye (and / or the photoluminescent wavelength converting film including the second organic photoluminescent dye) may have an absorption peak between about 400 and about 470 nm (blue light absorbing). In some forms, the second organic photoluminescent dye (and / or the photoluminescent wavelength converting film including the second organic photoluminescent dye) may have an emission peak between about 600 nm to about 660 nm. In some forms, the emission peak may be between about 600-605 nm, about 605-610 nm, about 610-615 nm, about 615-620 nm, about 620-625 nm, about 625-630 nm, about 630-635 nm, about 635-640 nm, about 640-645 nm, about 645-650 nm, about 650-655 nm, about 655-660 nm, or about 600 nm, about 610 nm, about 620 nm, about 630 nm, about 640 nm, about 650 nm, about 660 nm, or any wavelength in a range bounded by any of these values (red light emitting). In some forms, the emission spectrum of the second organic photoluminescent dye and / or the photoluminescent wavelength converting film may have a full width half maximum (FWHM) of less than about 65 nm, less than about 55 nm, less than about 50 nm, or less than about 45 nm.

[0038] In some forms, the second organic photoluminescent dye may be a photoluminescent dye described in co-pending U.S. Provisional Application No. 63 / 248,863, which is incorporated herein by reference for its discussion of photoluminescent dyes, U.S. Provisional Application No. 63 / 278,944, Attorney Docket No. N3252.10147US02, which is incorporated herein by reference, and PCT Patent Publication No. WO 2020 / 210761 , which is incorporated herein by reference. In some embodiments, the second organic photoluminescent dye may include one or more of RD- I-RD-10:

[0039]

[0040] In one or more forms, the first organic photoluminescent dye may absorb light from within the UV / blue absorption spectrum and emit light which has an emission spectra that has an overlap with the absorption spectra of the second dye, therefore enabling FRET transfer and enhancing the perceived emitted green light. In some forms, the second organic 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 one or more forms, the first organic photoluminescent dye and the second organic photoluminescent dye may absorb about 60-70% of a light source emitting light within the blue spectrum. In some embodiments, the resultant white light includes 30-50% blue light, 20-30% red light emitted from the wavelength converting film, and 20-30% green light emitted from the wavelength converting film. The thickness of the film may be adjusted to tune the percentage of blue light absorbed by the wavelength converting film and the percentage of blue light that passes through the wavelength converting film to include the resultant light. Depending on the number of times / layers printed, the amount of blue light that may be absorbed may be adjusted. For example, in some embodiments, the film may be sufficiently thick to absorb greater than about 75%, about 80%, about 90%, and / or about 95% of blue light. In some forms, the photoluminescent wavelength converting film may have a thickness of about 1-20 µm, about 20-30 µm, about 30-40 µm, or any thickness in a range bounded by any of these ranges. In some forms, the film and / or a layer containing the same may be deposited at the same position a number of times to increase the final thickness of the film and thus the amount of blue light absorbed at a particular selected position. In forms where a linking group is present, the length of the linking group may be tuned to optimize the solubility of the first organic photoluminescent dye and the second organic photoluminescent dye. In some forms, the solubility of the first organic photoluminescent dye and the second organic photoluminescent dye may be greater than about 0.15%. In some forms, the solubility of the first organic photoluminescent dye and the second organic photoluminescent dye may be about .03%-0.8%, about 0.8%-2%, or about 2%-3%, or any solubility in a range bounded by any of these ranges. The ratio of the amounts of a first blue absorber compound or moiety (e.g., the separate blue moiety) and a second blue absorber moiety (e.g., the blue absorber moiety in the blue absorber moiety-linking group-emitter moiety) may be adjusted to tune the color properties of the photoluminescent wavelength converting film. For example, the weight ratio of the first blue absorber moiety to the second blue absorber moiety may be about 0.01-100 (e.g., 1 mg of the first blue absorber moiety and 100 mg of the second blue absorber moiety yields 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, or about 0.43, about 0.91, about 1.8, about 3.0, or any weight ratio in a range bounded by any of these values. In some forms, the film may further include a transparent substrate, a translucent substrate, or a combination thereof. In some forms, the wavelength converting media may include scattering centers disposed within the film 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 (RI) different than the refractive index of the polymer matrix material. The scattering material may include materials whose refractive index (RI) is different from the RI of the polymer matrix. The scattering material may be useful in increasing external quantum yield, e.g., by reducing total internal reflection. In some forms, the difference in RI between the polymer matrix material 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, up to about 1 or about 2, although other variations are possible and contemplated. 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 include an oxide such as titanium dioxide (TiO2). 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 distal to a blue light emitting source, may have greater than 50% of the scattering centers. In some forms, the scattering centers may be uniformly distributed throughout the polymer matrix. In some forms, the film composition may not include the scattering centers described above. In these forms, a polymer layer including the scattering centers may be coated on a matte substrate. In some forms, a wavelength converting media may have an internal quantum yield (IQE) greater than about 0.8 (80%), about 0.81 (81%), about 0.82 (82%), about 0.83 (83%), about 0.84 (84%), about 0.85 (85%), about 0.86 (86%), about 0.87 (87%), about 0.88 (88%), about 0.89 (89%), about 0.9 (90%), about 0.91 (91%), about 0.92 (92%), about 0.93 (93%), about 0.94 (94%), or about 0.95 (95%), and may be up to nearly about 1 (100%), at the red or the green emission maximum. In some forms, a wavelength converting media may have an external quantum yield (EQE) greater than about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, or about 95%, and may be up to about 100%, at the red or the green emission maximum. Referring now to Fig.1, a display device 10 includes a light source 12 and a pixel film 16. In some forms, the pixel film 16 may be in optical communication with the light source 12, and enable an increased efficacy in transmitting light generated from the light source 12 to a viewer 20. Referring now to Fig.2, a display device 110 includes a light source 112. In one or more forms, the light source 112 may include a plurality of individual light sources, e.g., pixels, of the same or different colors such as red, green and / or blue (cyan). In some forms, the individual pixels may have a predetermined location within an intervening light source element. In some forms, the particular green and / or red individual pixels may have a predetermined location within an intervening light source element. In some forms, the film compositions or films incorporating film compositions described herein may be constructed or printed on a substrate or otherwise relocated using a printer having such predetermined locations and resolution, where the particle and film dot size may be substantially the same and / or location of a single pixel or dot printed or disposed within a film, printed element or substrate is according to the predetermined resolution and / or location.

[0041] The display device 110 also includes a back reflector 114, a pixel film 16, and a mask 118 which may be a color filter. In some forms, the pixel film 116 may be in optical communication with the light source 112, and enable an increased efficacy in transmitting light generated from the light source 112 to a viewed 20. In some forms, the pixel film 116 may be in optical communication with the light source 112, and / or interposed between the light source 112 and a viewer 120, and / or the mask 118, to enable an increased efficacy in transmitting the generated light from the light source 112 to the viewer 120.

[0042] In one embodiment, a backlit device backlit device includes a wavelength converting media or film composition as described herein.

[0043] In another embodiment, a method for making an LED light source includes making an undried wavelength shifting polymeric layer with an organic solvent and a photoluminescent dye described herein. In some forms, the method may include mixing a polymer and / or a monomer with an organic solvent. In some forms, the polymer and / or monomer precursor may be dispersed, dissolved and / or mixed with a solvent. In some forms, solvents may be used in the manufacture of material layers. In some forms, the solvent may be a non-polar solvent including, but not limited to, xylenes, cyclohexanone, acetone, toluene, methyl ethyl ketone, or combinations thereof. In some forms, the solvent may be a polar solvent including, but not limited to, ethanol, dimethylformamide (DMF), or a combination thereof. In some forms, the solvent may be a combination of non-polar and polar solvents.

[0044] In some forms, a polymer material described herein may include an aqueous solution of about 2 wt% to about 50 wt% polymer, about 2-5 wt%, about 5-10 wt%, about 10-15 wt%, about 15-20 wt%, about 20-25 wt%, about 25-30 wt%, about 30-35 wt%, about 35-40 wt%, about 40-45 wt%, about 45-50 wt%, about 2.5 to 30 wt%, about 5-15 wt%, about 15-25 wt%, about 25-35 wt%, or about 30 wt% polymer, or about any value in a range bounded by any of these values.

[0045] Hereinafter, embodiments and methods will be described in more detail. EXAMPLES It has been discovered that embodiments of the wavelength converting pixel film described herein have improved performance as compared to other forms of color conversion films. These benefits are further demonstrated by the following examples, which are intended to be illustrative of the disclosure only but are not intended to limit the scope or underlying principles in any way. Synthesis of blue absorber compound 1.1 Synthesis of Compound BAC2-1 Compound BAC2-2.2 (5,11-dibromo-1H,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. To the flask was added 1H,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), followed by 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) was obtained (Both had similar LCMS and NMR. MS (APCI): calculated for Chemical Formula: C18H6Br2O4(M+H) = 445; found: 445. 1H NMR (400 MHz, TCE) δ 9.47 (dd, J = 8.4, 1.5 Hz, 1H), 8.76 (d, J = 14.2 Hz, 2H), 7.72 – 7.63 (m, 1H), 7.56 (dd, J = 8.3, 1.4 Hz, 1H), 7.46 (ddd, J = 8.5, 6.7, 1.9 Hz, 1H). Compound BAC2-1.2: A mixture of compound BAC2-1.1 (2.066 g, 4.6 mmol), 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, stirred for 5 min. The resultant mixture was filtered, a yellow solid was collected, and dried in vacuum to afford 1.57 g desired product. The filtrate solution was washed with water (200 mL), and 5% Na2CO3aqueous solution (150 mL x 3). The organic phase was collected, dried over MgSO4, 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). 1H NMR (400 MHz, CDCl3) δ 9.54 (dd, J = 8.4, 1.5 Hz, 1H), 8.87 (d, J = 14.7 Hz, 2H), 7.66 (ddd, J = 8.4, 7.1, 1.5 Hz, 1H), 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). Compound BAC2-1: A mixture of compound 1758-14 (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, 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). LCMS (APCI-): Calcd for C46H29F12NO3(M-) = 871.2; Found: 871. 1H NMR (400 MHz, CDCl3) δ 8.81 (s, 1H), 8.56 (s, 1H), 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, 1H), 7.07 – 6.95 (m, 2H), 2.86 – 2.65 (m, 2H), 1.21 (dd, J = 6.9, 3.6 Hz, 12H). 1.3 Synthesis of Compound BAC2-2 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 ºC 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 / DCM (0% to 100% DCM). The main peak was collected, and removal of solvents gave a yellow solid, which was washed with MeOH, and then filtered and dried in air to give a bright yellow solid (BAC2-2) (0.38 g, in 85% yield). LCMS (APCI-): Calcd for C44H31F6NO3(M-) = 735.22; Found: 735. 1H NMR (400 MHz, CDCl3) δ 8.77 (s, 1H), 8.54 (s, 1H), 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, 1H), 7.42 (ddd, J = 8.5, 7.2, 1.5 Hz, 1H), 7.36 (d, J = 7.8 Hz, 2H), 7.30 (d, J = 1.3 Hz, 1H), 7.16 (dd, J = 8.3, 1.5 Hz, 1H), 6.95 (ddd, J = 8.3, 7.1, 1.4 Hz, 1H), 2.77 (p, J = 6.8 Hz, 2H), 1.20 (dd, J = 6.8, 3.7 Hz, 12H). Compound BAC2-3: : A mixture of compound BAC2-1.2 (0.4g, 0.66 mmol), (phenyl)boronic acid (0.244 g, 2.0 mmol), Pd(PPh3)4(58 mg, 0.05 mmol), and K2CO3(276 mg, 2.0 mmol) in dioxane / water (9 mL / 1 mL) was heated at 100 ºC 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 / DCM (0% to 100% DCM). The main peak was collected, and removal of solvents gave a yellow solid, which was washed with MeOH, and then filtered and dried in air to give a bright yellow solid (0.37 g, in 93% yield). LCMS (APCI-): Calcd for C42H33NO3(M-) = 599.25; Found: 599. 1H NMR (400 MHz, CDCl3) δ 8.77 (s, 1H), 8.56 (s, 1H), 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, 1H), 2.79 (p, J = 6.8 Hz, 2H), 1.20 (dd, J = 6.8, 2.7 Hz, 12H). Synthesis of Compound BAC2-4 BAC2-4.1: To a solution of compound BAC2-1.1 (1.0 g, 2.23 mmol) in 6 mL 96% concentrated sulfuric acid, NBS (0.5 g, 2.8 mmol) was added. 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 and then dried in vacuum to give a yellow solid (1.16 g, in quantitative yield). LCMS (APCI-): calcd for C18H5Br3O4= 521.77; found: 521.7.1H NMR (400 MHz, CDCl3) δ 9.69 (d, J = 2.2 Hz, 1H), 8.88 – 8.76 (m, 2H), 7.77 (dd, J = 8.7, 2.3 Hz, 1H), 7.72 – 7.50 (m, 1H), 7.44 (d, J = 8.7 Hz, 1H). 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 DCM, washed with water (200 mL x 2) and 5% NaHCO3(100 mL x 2), dried over MgSO4, and then loaded on silica gel and purified by flash chromatography using eluents of hexanes / DCM (0% to 60% DCM). The 1st main peak was collected, then removal of the solvents gave a yellow solid (1.0 g, in 66.4% yield). LCMS (APCI-): calcd for C30H22Br3NO3= 680.91; Found: 680.8.1H NMR (400 MHz, CDCl3) δ 9.90 – 9.46 (m, 1H), 8.98 – 8.77 (m, 2H), 7.90 – 7.64 (m, 1H), 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). BAC2-4: A mixture of compound BAC2-4.1 (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 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 and then submitted for another chromatography separation using eluents of hexanes / toluene (0% to 80% toluene). The 1st main 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: 879.1.1H NMR (400 MHz, TCE) δ 8.64 (s, 1H), 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, 1H), 7.50 – 7.36 (m, 4H), 7.31 (d, J = 8.6 Hz, 1H), 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). Synthesis of Compound BAC2-5

[0046] BAC2-5.1: 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, 50mL 20% hydrochloride acid aqueous solution was added dropwise to the solution followed by the addition of 50 mL water. The resulting mixture was allowed to stand for 3 hrs, then filtered to collect the precipitate, which was dried in vacuum to afford 4.6g 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 the desired product (3.3g, in 80% yield). LCMS (APCI+): calcd for C18H9BrNO6(M+H) = 413.95; Found: 414.1H NMR (400 MHz, TCE-d2) δ 8.70 (dd, J = 8.4, 1.2 Hz, 1H), 8.63 (dd, J = 7.3, 1.2 Hz, 1H), 8.41 (d, J = 8.3 Hz, 1H), 8.24 (d, J = 2.4 Hz, 1H), 7.89 – 7.79 (m, 2H), 7.20 (d, J = 8.7 Hz, 1H), 6.82 (d, J = 8.3 Hz, 1H). BAC2-5.2: A mixture of compound BAC2-5.1 (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 vacuum to give a solid (1.35 g, in 82% yield). LCMS (APCI-): calcd for C18H10BrNO4= 382.98; Found: 383.1H NMR (400 MHz, DMSO-d6) δ 9.01 – 8.26 (m, 3H), 7.96 (s, 1H), 6.93 (dd, J = 85.2, 36.5 Hz, 4H), 5.54 (s, 2H). BAC2-5.3: Compound BAC2-5.2 (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 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 × 3), and then stirred in 50 mL 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) δ 8.51 (dd, J = 12.3, 8.1 Hz, 2H), 8.12 (d, J = 2.3 Hz, 1H), 7.86 (d, J = 7.9 Hz, 1H), 7.60 (dd, J = 8.8, 2.3 Hz, 1H), 7.28 (d, J = 8.3 Hz, 1H), 7.23 (d, J = 8.8 Hz, 1H). BAC2-5.4 (5,9,11-tribromo-1H,3H-isochromeno[6,5,4-mna]xanthene-1,3-dione): 9- bromo-1H,3H-isochromeno[6,5,4-mna]xanthene-1,3-dione (compound BAC2-5.3) (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, stirred for 15 minutes, and the resulting precipitate was then filtered off, washing with water. The precipitate was dried in a vacuum oven at 80 °C to give a brownish solid, assume 100%, taken directly to the next step. LCMS showed a mixture of tri- and tetra-bromo isomers. Too insoluble for NMR. BAC2-5.5 (5,7,9,11-tetrabromo-2-(2,6-diisopropylphenyl)-1H-xantheno[2,1,9- def]isoquinoline-1,3(2H)-dione): Compound BAC2-5.4 (assume 100% yield, 5.000 mmol, 2625 mg) was stirred with 2,6-diisopropylaniline (50.00 mmol, 9.4 mL) in 50 mL of propionic acid under argon overnight at 150 °C. The mixture was cooled to room temperature, diluted with water, acidified to pH ~1 with 6N HCl, and then more water added (~300 mL) to precipitate the product). The precipitate was taken up in methanol, added ~25% v / v water, the resulting precipitate filtered off again, and dried in a vacuum oven at 80 °C to give a mixture of tri- and tetra-bromoimides, same ratio as in previous step. It was used in the next step without further purification. Assume 100% yield. BAC2-5 (5,9,11-tris(3,5-bis(trifluoromethyl)phenyl)-2-(2,6-diisopropylphenyl)-1H- xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione): Compound BAC2-5.5 (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-, rest tri-). The reaction mixture was cooled to room temperature, the THF removed in vacuo, the residue taken up in DCM / water and filtered through a polypropylene frit to retain water, eluting with DCM. To the DCM was added ~45g of flash silica gel, the solvent was removed in vacuo, and the silica packed into a loading tube and was 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 is a mixture of isomers by NMR. 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: 1084.1H NMR (400 MHz, TCE) δ 8.79 (s, 1H), 8.55 (s, 1H), 8.32 – 8.27 (m, 2H), 8.16 (s, 1H), 8.12 (d, J = 1.6 Hz, 2H), 8.06 (s, 1H), 7.84 (s, 1H), 7.75 (dd, J = 8.6, 2.2 Hz, 1H), 7.49 (t, J = 7.8 Hz, 1H), 7.44 – 7.37 (m, 3H), 7.34 (d, J = 7.8 Hz, 2H), 7.28 (d, J = 2.2 Hz, 1H), 3.46 (s, 4H), 2.71 (h, J = 6.8 Hz, 2H), 1.18 (dd, J = 6.9, 3.6 Hz, 12H). Synthesis of Compound BAC2-6 BAC-2-6.2 (5,11-dibromo-1H,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. To the flask was added 1H,3H-isochromeno[6,5,4-mna]xanthene-1,3-dione (synthesized by an outside laboratory) (34.688 mmol, 10.00 g), followed by ortho-dichlorobenzene (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 with an aluminum heat block 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 to provide orangish solids, 10.866 g total (69.9% yield). Both had the same LCMS and NMR. MS (APCI): calculated for Chemical Formula: C18H6Br2O4(M+H) = 445; found: 445.1H NMR (400 MHz, TCE) δ 9.47 (dd, J = 8.4, 1.5 Hz, 1H), 8.76 (d, J = 14.2 Hz, 2H), 7.72 – 7.63 (m, 1H), 7.56 (dd, J = 8.3, 1.4 Hz, 1H), 7.46 (ddd, J = 8.5, 6.7, 1.9 Hz, 1H). BAC-2-6.3 (5,11-dibromo-2-(2-ethylhexyl)-1H-xantheno[2,1,9-def]isoquinoline- 1,3(2H)-dione): BAC-2-6.2 (7.278 mmol, 3.261 g), 2-ethylhexan-1-amine (14.556 mmol, 2.4 mL), and DMAP (2.183 mmol, 267 mg) were combined in a 2N 100 mL RBF under argon in anhydrous DMF (30 mL) and stirred at 120 °C for 2 hours. The crude reaction mixture was quenched with 6N HCl until pH 1, then diluted with water (~100 mL). The resulting precipitate was filtered off, and washed with water. The compound was dried by suction for several hours, then split into two equal portions and used in subsequent reactions without further purification. Assume 100% yield for the next step. MS (APCI): calculated for Chemical Formula: C26H23Br2NO3(M+H) = 556; found: 556. BAC-2-6 (2-(2-ethylhexyl)-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9- def]isoquinoline-1,3(2H)-dione): BAC-2-6.3 (3.693 mmol, 2.035 g), (4- (trifluoromethyl)phenyl)boronic acid (14.556 mmol, 2.764 g), K2CO3(20.015 mmol, 2.766 g), and Pd(dppf)Cl2(0.255 mmol, 186 mg) were combined in a 250 mL 2N RBF in THF (60 mL), DMF (12 mL), and water (6 mL) and stirred under argon at 80 °C for 5 hours. The crude reaction mixture was evaporated to dryness in vacuo. The residue was taken up in DCM and evaporated onto ~20g of flash silica gel in vacuo and placed in a loader. It was purified by flash chromatography on silica gel (220g, equilibrate 50% hexane / DCM, eluting 50% (2 CV) → 100% DCM (20 CV)). Fractions containing product were evaporated to dryness in vacuo to give a yellow solid, 2.070 g (82% yield from BAC-2.2. MS (APCI): calculated for Chemical Formula: C40H31F6NO3(M+H) = 688; found: 688.1H NMR (400 MHz, TCE) δ 8.70 (s, 1H), 8.45 (s, 1H), 7.91 (d, J= 8.2 Hz, 2H), 7.83 (dd, J= 8.3, 6.6 Hz, 4H), 7.65 (d, J= 8.0 Hz, 2H), 7.39 (ddd, J= 8.5, 7.1, 1.5 Hz, 1H), 7.28 (dd, J= 8.3, 1.3 Hz, 1H), 7.09 (dd, J= 8.4, 1.5 Hz, 1H), 6.93 (ddd, J = 8.4, 7.1, 1.3 Hz, 1H), 4.22-3.99 (m, 2H), 1.95 (hept, J = 3.7 Hz, 1 H), 1.49 - 1.22 (m, 8H), 1.00 - 0.83 (m, 6H).

[0047] Synthesis of BAC2-7, BAC2-10, and BAC2-13:

[0048] Compound BAC2-7-1 (6-(4-bromo-2-nitrophenoxy)-1H,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 C18H9BrNO6(M+H) = 413.95; Found: 414.1H NMR (400 MHz, TCE-d2) δ 8.70 (dd, J = 8.4, 1.2 Hz, 1H), 8.63 (dd, J = 7.3, 1.2 Hz, 1H), 8.41 (d, J = 8.3 Hz, 1H), 8.24 (d, J = 2.4 Hz, 1H), 7.89 – 7.79 (m, 2H), 7.20 (d, J = 8.7 Hz, 1H), 6.82 (d, J = 8.3 Hz, 1H). Compound BAC2-7-2 (6-(2-amino-4-bromophenoxy)-1H,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 C18H10BrNO4= 382.98; Found: 383.1H NMR (400 MHz, DMSO-d6) δ 9.01 – 8.26 (m, 3H), 7.96 (s, 1H), 6.93 (dd, J = 85.2, 36.5 Hz, 4H), 5.54 (s, 2H). Compound BAC2-7-3 (9-bromo-1H,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 × 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) δ 8.51 (dd, J = 12.3, 8.1 Hz, 2H), 8.12 (d, J = 2.3 Hz, 1H), 7.86 (d, J = 7.9 Hz, 1H), 7.60 (dd, J = 8.8, 2.3 Hz, 1H), 7.28 (d, J = 8.3 Hz, 1H), 7.23 (d, J = 8.8 Hz, 1H). Compound BAC2-7-4 (5,9,11-tribromo-1H,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. 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 1L 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) δ 6.36 (s, 2H), 2.15 (hept, J = 6.9 Hz, 1H), 1.94 (hept, J = 6.8 Hz, 2H), 0.46 (d, J = 6.9 Hz, 6H), 0.43 (d, J = 7.0 Hz, 12H). 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) δ 6.03 (s, 2H), 2.21 (hept, J = 6.8 Hz, 2H), 1.96 (hept, J = 7.0 Hz, 1H), 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. Compound BAC2-7-7 (5,9,11-tribromo-2-(2,4,6-triisopropylphenyl)-1H- 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 (1L) 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. Compound BAC2-7 (5,9,11-tris(4-(trifluoromethyl)phenyl)-2-(2,4,6- triisopropylphenyl)-1H-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)Cl2(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 CV) → 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) δ 8.61 (s, 1H), 8.39 (s, 1H), 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, 1H), 7.31 – 7.22 (m, 3H), 7.20 (s, 2H), 2.97 (h, J = 6.9 Hz, 1H), 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). 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. 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) δ 8.48 (s, 1H), 8.42 (s, 1H), 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, 1H), 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). Synthesis of BAC2-9, BAC2-12, and BAC2-15: Compound BAC2-9 (5,9,11-tris(3,5-bis(trifluoromethyl)phenyl)-2-(2,4,6- triisopropylphenyl)-1H-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)Cl2(1.652 mmol, 1209 mg) were stirred in dry THF (150 mL) and water (20 mL) under argon at 80 ℃ 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) δ 8.76 (s, 1H), 8.64 (d, J = 1.7 Hz, 2H), 8.54 (d, J = 1.7 Hz, 2H), 8.52 (s, 1H), 8.27 (s, 1H), 8.20 (s, 1H), 8.11 (dd, J = 8.7, 2.2 Hz, 1H), 8.07 (s, 1H), 7.58 (d, J = 1.6 Hz, 2H), 7.43 (s, 1H), 7.39 (d, J = 8.6 Hz, 1H), 7.34 (d, J = 1.5 Hz, 1H), 7.32 (d, J = 2.2 Hz, 1H), 7.20 (s, 2H), 2.98 (hept, J = 7.0 Hz, 1H), 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). 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. 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) δ 8.77 – 8.70 (m, 1H), 8.66 – 8.55 (m, 1H), 8.34 – 8.21 (m, 2H), 8.17 (d, J = 13.9 Hz, 1H), 8.10 (d, J = 8.0 Hz, 1H), 8.00 (d, J = 22.9 Hz, 1H), 7.85 – 7.75 (m, 2H), 7.72 – 7.58 (m, 1H), 7.46 – 7.36 (m, 1H), 7.36 – 7.29 (m, 1H), 7.16 (d, J = 1.5 Hz, 2H), 7.10 – 6.94 (m, 2H), 3.00 (p, J = 6.9 Hz, 1H), 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). Synthesis of BAC2-8, BAC2-11, and BAC-14 Compound BAC2-8 (5,9,11-tris(3-(trifluoromethyl)phenyl)-2-(2,4,6- triisopropylphenyl)-1H-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)Cl2(1.652 mmol, 1209 mg) were stirred in dry THF (150 mL) and water (20 mL) under argon at 80 ℃ 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) δ 8.73 (s, 1H), 8.51 (s, 1H), 8.12 (d, J = 2.1 Hz, 1H), 8.07 – 7.97 (m, 1H), 7.93 – 7.72 (m, 6H), 7.67 (dd, J = 8.6, 2.1 Hz, 1H), 7.58 (d, J = 7.8 Hz, 1H), 7.48 (t, J = 7.8 Hz, 1H), 7.41 – 7.32 (m, 3H), 7.16 (s, 2H), 7.13 (d, J = 2.4 Hz, 1H), 2.99 (hept, J = 6.9 Hz, 1H), 2.70 (h, J = 6.8 Hz, 2H), 1.34 (d, J = 6.9 Hz, 6H), 1.17 (dd, J = 6.8, 2.7 Hz, 12H). BAC2-11 Compound BAC2-11 (5,7,9,11-tetrakis(3-(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-(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. Synthesis of BAC2-14 Compound BAC2-14 (5,9,11-tris(3-(trifluoromethyl)phenyl)-2-(2,4,6- triisopropylphenyl)-1H-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) δ 8.46 (s, 1H), 8.41 (s, 1H), 8.13 (d, J = 7.8 Hz, 1H), 8.05 (s, 1H), 7.84 (s, 2H), 7.72 (s, 1H), 7.57 (d, J = 8.0 Hz, 2H), 7.48 (d, J = 7.9 Hz, 1H), 7.43 – 7.10 (m, 11H), 6.90 (d, J = 6.8 Hz, 2H), 2.98 (h, J = 6.9 Hz, 1H), 2.64 (s, 2H), 1.29 (d, J = 6.9 Hz, 6H), 1.08 (d, J = 6.7 Hz, 12H). Synthesis of BAC2-16 Compound BAC2-16.1: 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 ºC 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 C18H4Br4O4(M-) = 599.68; Found: 600.1H NMR (400 MHz, CDCl3) δ 9.79 (d, J = 4.2 Hz, 1H), 8.82 – 8.76 (m, 3H). Compound BAC2-16.2: A mixture of compound BAC2-16.1 (1.3 g, 2.15 mmol) and 2,6- diisopropylaniline (3 mL, 15.6 mmol) in propionic acid (25 mL) was heated at 170 ºC overnight. The resulting mixture was diluted with 200 mL DCM, then washed with water (200 mL x 2) and 5% NaHCO3(100 mL x 2), then dried over MgSO4, 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). LCMS (APCI-): calcd for C30H21Br4NO3= 758.83; Found: 759. Compound BAC2-16: A mixture of compound BAC2-16.2 (0.68 g, 0.89 mmol), 4- trifluoromethylphenylboronic acid (1.709 g, 9 mmol), Pd(PPh3)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 ºC 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). LCMS (APCI-): calcd for C58H37F12NO3= 1023.26; Found: 1023. 1H NMR (400 MHz, CDCl3) δ 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). Synthesis of BAC2-17 Compound BAC2-17: A mixture of compound BAC2-17-1 (0.37g, 0.61 mmol), (3- (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 ºC 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). LCMS (APCI-): Calcd for C44H31F6NO3(M-) = 735.22; Found: 735. 1H NMR (400 MHz, TCE) δ 8.63 (s, 1H), 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 Hz, 1H), 6.84 (ddd, J = 8.4, 7.1, 1.4 Hz, 1H), , 2.64 (p, J = 6.8 Hz, 2H), 1.08 (dd, J = 6.9, 3.0 Hz, 12H). Synthesis of first photoluminescent dye and second photoluminescent dye Synthesis procedure for GN-1

[0049] 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 ºC overnight under an argon atmosphere. After being cooled down to room temperature, 50 mL of 20% hydrochloride acid aqueous solution was added dropwise to the solution, and then 50 mL of water was added. The resulting mixture was allowed to stand for 3 hrs., then filtered to collect the precipitate, which was dried in vacuum to afford 4.6g of crude product. The crude product was dispersed in 30 mL of acetone and stirred overnight at room temperature to dissolve the impurities. After filtration and drying in vacuum, a brown, yellow solid product resulted (3.3g, in 80% yield). LCMS (APCI+): calculated for C18H9BrNO6(M+H) = 413.95; Found: 414.1H NMR (400 MHz, TCE-d2) δ 8.70 (dd, J = 8.4, 1.2 Hz, 1H), 8.63 (dd, J = 7.3, 1.2 Hz, 1H), 8.41 (d, J = 8.3 Hz, 1H), 8.24 (d, J = 2.4 Hz, 1H), 7.89 – 7.79 (m, 2H), 7.20 (d, J = 8.7 Hz, 1H), 6.82 (d, J = 8.3 Hz, 1H). Compound GN-1.2: A mixture of compound GN-1.1 (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-): calculated for C18H10BrNO4= 382.98; Found: 383.1H NMR (400 MHz, DMSO-d6) δ 9.01 – 8.26 (m, 3H), 7.96 (s, 1H), 6.93 (dd, J = 85.2, 36.5 Hz, 4H), 5.54 (s, 2H). Compound GN-1.3: Compound GN-1.2 (2.65g, 6.9mmol) was dispersed in acetic acid (50mL) and 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 transferred into an additional funnel, and dropped into a copper sulfate solution (12g, 47 mmol, in 140 mL water) for over a one-hour period at 130 °C. After being cooled to room temperature, the precipitate was collected by filtration, washed with water (100mL × 3), and then stirred in 50 mL of acetone at 40 °C for 30 min. After filtration, drying in air and then vacuum, a brown, yellow solid was provided (1.76g, in 70% yield). LCMS (APCI+): calculated for C18H8BrO4(M+H) = 366.95; Found: 367.1H NMR (400 MHz, d2-TCE) δ 8.51 (dd, J = 12.3, 8.1 Hz, 2H), 8.12 (d, J = 2.3 Hz, 1H), 7.86 (d, J = 7.9 Hz, 1H), 7.60 (dd, J = 8.8, 2.3 Hz, 1H), 7.28 (d, J = 8.3 Hz, 1H), 7.23 (d, J = 8.8 Hz, 1H). Synthesis procedure for Compound GN-1.6

[0050] A mixture of ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (1.0g, 6.0 mmol), 4-hydroxy-2,6- dimethylbenzaldehyde (0.449g, 3.0 mmol) and p-toluenesulfonic acid (p-TsOH) (50 mg, 0.29mmol) in 50 mL dichloroethane (DCE) was degassed and stirred at room temperature overnight. Liquid chromatography-Mass spectroscopy (LCMS) analysis shows that the reaction was completed with main leak of m / e+= 467. To the mixture obtained above, 2,3- Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) (0.817g, 3.6 mmol) was added and the whole was stirred at room temperature for 30 min. LCMS analysis indicates that reaction was completed with a main peak of m / e+= 465. With ice-batch cooling, to the mixture obtained above, triethylamine (1.7 mL, 12 mmol) and BF3-diethyl ether (2.2 mL, 18 mmol) was added, and the resulting mixture was stirred at 50 °C for one hour. Additional 1mL of triethylamine and 1mL of BF3-diethyl ether were added, and the whole was heated for an additional one hour. LCMS analysis indicates that all dipyrrolemethine starting material was converted to BODIPY product with m / e+= 513. After being cooled to room temperature, the reaction mixture was submitted to silica gel and purified by flash chromatography using eluents of hexanes / ethyl acetate (0% to 30% ethyl acetate). The desired fraction was collected. After removal of solvents, the desired product was obtained as an orange solid (1.0g, in 65% yield).1H NMR (400 MHz, Chloroform-d) δ 6.68 (s, 2H), 4.29 (q, J = 7.1 Hz, 4H), 2.84 (s, 6H), 2.05 (s, 6H), 1.34 (t, J = 7.1 Hz, 6H). LCMS (APCI+): calculated for C27H32BF2N2O5(M+H) = 513.2; Found: 513. Procedure of GN-1.4 synthesis – 2-(4-(9-bromo-1,3-dioxo-1H-xantheno[2,1,9- def] isoquinolin-2(3H)-yl)phenyl)acetic acid: A mixture of GN-1.3 (400.0 mg, 1.1 mmol), 4-aminophenylacetic acid (329.4 mg, 2.2 mmol) and DMAP (9.3 mg, 0.080 mmol) in DMF (8 mL) was degassed at room temperature. Then the mixture was heated up to 165 °C and kept at this temperature for 3 hrs. TLC and LCMS showed ~95% conversion without observable side-reaction. The mixture was cooled down to 50 °C. Then it was poured into an acetone solution (40 mL), which was pre-chilled by a water-ice bath. The mixture was kept at 0 °C for 2 hrs. and then stirred at room temperature overnight. The solid was collected through vacuum filtration and washed by acetone (4 mL) and it was dried by vacuum oven at 100 °C for 3 hours to provide the pure compound GN-1.4 as a yellow brown solid 395.0 mg, 73% yield. MS (APCI): calculated for C26H14BrNO5([M+H]+) = 500 found: 500.1H NMR (400 MHz, CDCl2CDCl2) δ 8.65 (d, J = 8.0 Hz, 1H), 8.62 (d, J = 8.0 Hz, 1H), 8.21 (dd, J = 6.4 Hz, 2.4 Hz, 1H), 7.99 (bs, 1H), 7.95 (t, J = 7.6 Hz, 1H), 7.67 (dd, J = 8.4 Hz, 2.4 Hz, 1H), 7.53 (d, J = 8.0 Hz, 2H), 7.37 (d, J = 8.4 Hz, 1H), 7.32 (m, 3H), 2.94 (s, 2H). Procedure of compound GN-1.5 synthesis – 2-(4-(1,3-dioxo-9-(4- (trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid: A 100 mL vial was fitted with a stir bar. In the vial, a mixture of compound GN-1.4 (400.0 mg, 0.80 mmol), 4-(trifluoromethyl)phenylboronic acid (262.2 mg, 1.6 mmol), Pd(dppf)Cl2(41.0 mg, 0.056 mmol) and K2CO3(298.0 mg, 2.2 mmol) in THF / DMF / H2O (22 ml / 4.4 ml / 2.2 ml) was degassed at room temperature. The reaction mixture was heated up to 80 °C and the reaction was kept at this temperature overnight. TLC was used to monitor the reaction. After the completion, the reaction was worked up by the addition of 0.1N HCl (150 ml) and EtOAc (150 ml). The aqueous phase was further extracted by THF (150 ml*3). The combined organic phases were dried over anhydrous Na2SO4, concentrated under rotavapor, and purified by flash chromatography, using DCM in EtOAc (0-40%, with 0.1% TFA) as an eluant to provide the pure RL-naphthalimide derivative GN-1.5 as a yellow / yellow brown solid.363.0 mg, 80% yield. MS (APCI): calculated for C33H18F3NO5([M+H]+) = 566 found: 566.1H NMR (400 MHz, DMSO-d6) 8.76 (m, 1H), 8.56 (m, 2H), 8.52 (dd, J = 8.0 Hz, J = 3.2 Hz, 1H), 8.15 (m, 2H), 8.06 (m, 1H), 7.94 (d, J = 8.0 Hz, 2H), 7.66 (dd, J = 8.0 Hz, J = 4.0 Hz, 1H), 7.53 (m, 1H), 7.45 (d, J = 8.0 Hz, 2H), 7.33 (d, J = 8.0 Hz, 2H), 3.72 (s, 2H). Procedure for Compound GN-1: A mixture of compound GN-1.5 (50 mg, 0.089 mmol), compound GN-1.6 (30 mg, 0.059 mmol), DMAP / TsOH salt (15 mg, 0.051 mmol) and EDC•HCl (60 mg, 0.31 mmol) in 5 mL DCM was stirred at room temperature overnight. The reaction mixture was submitted to silica gel and purified by flash chromatography using eluents of DCM / ethyl acetate (0% to 10% ethyl acetate). The desired product peak was collected and concentrated under reduced pressure. The resulting solid was reprecipitated with ethyl acetate / methanol and dried in air to give an orange solid (45mg, in 72%). LCMS (APCI-): calculated for C60H47BF5N3O9: 1059.33; Found: 1059.1H NMR (400 MHz, Methylene Chloride-d2) δ 8.73 (d, J = 7.9 Hz, 1H), 8.66 (d, J = 8.3 Hz, 1H), 8.39 (d, J = 2.2 Hz, 1H), 8.17 (d, J = 8.0 Hz, 1H), 7.86 (dt, J = 11.4, 8.4 Hz, 5H), 7.64 (d, J = 8.3 Hz, 2H), 7.57 (d, J = 8.6 Hz, 1H), 7.43 (d, J = 8.3 Hz, 1H), 7.41 – 7.35 (m, 2H), 7.09 (s, 2H), 4.30 (q, J = 7.1 Hz, 4H), 4.05 (s, 2H), 2.84 (s, 6H), 2.18 (s, 6H), 1.77 (s, 6H), 1.36 (t, J = 7.1 Hz, 6H). Synthesis procedure for GN-2 GN-2.1 ((3,5-dibromophenoxy)triethylsilane): A 500 mL 2N round bottom flask was charged with a stir bar and fitted with a gas adapter and septum. The flask was placed in a Dewar bowl. The flask was flushed with argon. To the flask was added 3,5- dibromophenol (100.0 mmol, 25.190g), imidazole (300.0 mmol, 20.430 g), and dry DCM (200 mL). The mixture was stirred to get a solution at room temperature, then cooled to 0 °C with an ice-water bath. To the flask was added chlorotriethylsilane (150.0 mmol, 25.2 mL) via syringe with stirring at 0 °C. The reaction was stirred at 0 °C for 50 minutes, then partitioned with water (200 mL). The layers were separated, and the water layer was extracted with DCM (50 mL). The combined organic layers were dried over MgSO4, filtered and evaporated to dryness in vacuo. The mixture was diluted with hexanes and loaded onto a loader containing 60g of flash silica gel and purified by flash chromatography on silica gel (220g, equilibrate and elute 100% hexanes). Fractions containing product were evaporated to dryness in vacuo to give a colorless oil, 27.811 g (76% yield). MS (APCI): calculated for Chemical Formula: C12H18Br2OSi (M+H) = 365; found: 365.1H NMR (400 MHz, TCE) δ 7.28 (t, J = 1.7 Hz, 1H), 6.96 (d, J = 1.6 Hz, 2H), 1.10 – 0.95 (m, 9H), 0.75 (qd, J = 7.7, 0.9 Hz, 6H). GN-2.2 (2,6-dibromo-4-hydroxybenzaldehyde): A 250 mL 2N round bottom flask was charged with a stir bar and fitted with a gas adapter and septum. The flask was placed in a Dewar bowl. The flask was flushed with argon. Weighed out GN-2.1 (30.00 mmol, 10.985 g) and azeotroped from toluene. GN-2.1 was transferred under argon to the reaction flask, then dry THF was added (130 mL) and the reaction mixture was stirred to get a homogeneous solution at room temperature. The reaction mixture was cooled to - 78 °C (dry ice / acetone). The system was purged of oxygen by vacuum / backfilling argon cycles (3X). A solution of LDA in THF / hexanes (1.0M, 60.00 mmol, 60.0 mL) was added with vigorous stirring over a few minutes. The solution was stirred at -78 °C for 70 minutes, then anhydrous DMF (150.0 mmol, 11.6 mL) was added via syringe and stirred for 60 minutes at -78 ° C. The reaction mixture was dumped cold into 400 mL of sat. NH4Cl solution with stirring. The solution was extracted with EtOAc (100 mL), and the layers separated. The aqueous layer was acidified to pH ~1 using excess 6N HCl to get an off- white ppt. The organic layer was extracted with 100 mL sat. NH4Cl, then twice with 10% K2CO3(100 mL). These aqueous extracts were also added to the acidified water, maintaining pH ~1. The resulting precipitate was filtered off, then dried in a vacuum oven at 90 °C overnight to give an off-white / grey precipitate, 6.665 g (79% yield). MS (APCI): calculated for Chemical Formula: C7H4Br2O2(M+H) = 281; found: 281.1H NMR (400 MHz, Acetone) δ 10.14 (s, 1H), 7.24 (s, 2H). GN-2.3 (3,3'',5,5''-tetra-tert-butyl-5'-hydroxy-[1,1':3',1''-terphenyl]-2'-carbaldehyde): A 500 mL 2N round bottom flask was charged with a stir bar and fitted with a finned condenser / gas adapter and flow control. The system was flushed with argon. GN-2.2 (5.500 mmol, 1.540 g), (3,5-di-tert-butylphenyl)boronic acid (22.00 mmol, 5.150g), NaHCO3(33.00 mmol, 2.772 g), Pd(dppf)Cl2(1.100 mmol, 805 mg), dry THF (270 mL), and water (9 mL) were added to the flask. The heat block was set to 80 °C and the reaction mixture stirred at this temperature overnight. The reaction mixture was evaporated onto 60g of flash silica gel and placed into a loader and purified by flash chromatography on silica gel (220g, equilibrate 0% EtOAc / hexanes, eluting 0% (2 CV) → 30% EtOAc / hexanes (20 CV)). Fractions containing product were evaporated to dryness in vacuo to give a light yellow solid, 2.256 g (82% yield). MS (APCI): calculated for Chemical Formula: C35H46O2(M+H) = 499; found: 499.1H NMR (400 MHz, TCE) δ 9.80 (s, 1H), 7.42 (t, J = 1.8 Hz, 2H), 7.15 (d, J = 1.8 Hz, 4H), 6.87 (s, 2H), 1.35 (s, 36H). GN-2.4 (3,3'',5,5''-tetra-tert-butyl-2'-formyl-[1,1':3',1''-terphenyl]-5'-yl 2-(4-(5,11- bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin- 2(3H)-yl)phenyl)acetate): A 40 mL screw-cap vial was charged with a stir bar, and GN- 2.3 (4.523 mmol, 2256 mg), (2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H- xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid (from outside vendor) (5.428 mmol, 4.590 g), DMAP.pTsOH salt (4.523 mmol, 1332 mg), and dry DCM (20 mL) were added. The reaction mixture was stirred at room temperature to give a yellow slurry. With stirring at room temperature, DIC (9.047 mmol, 1.41 mL) was added. The reaction mixture was stirred at room temperature for 60 minutes, then diluted with hexanes 1:1 and loaded onto ~60g of flash silica gel packed into a loader and purified by flash chromatography on silica gel (220g, equilibrate 0% EtOAc / hexanes, eluting 0% 2 CV → 20% EtOAc / hexanes (22 CV)). Fractions containing product were evaporated to dryness in vacuo to give a yellow solid, 5.182 g (86% yield). MS (APCI): calculated for Chemical Formula: C77H63F12NO6(M+H) = 1326; found: 1326.1H NMR (400 MHz, TCE) δ 9.89 (s, 1H), 8.75 (s, 1H), 8.50 (s, 1H), 8.29 – 8.24 (m, 2H), 8.07 (s, 1H), 8.05 – 7.97 (m, 3H), 7.67 – 7.60 (m, 2H), 7.49 (ddd, J = 8.6, 6.1, 2.6 Hz, 1H), 7.43 (t, J = 1.8 Hz, 2H), 7.38 (d, J = 8.4 Hz, 2H), 7.31 – 7.25 (m, 1H), 7.23 (s, 2H), 7.17 (d, J = 1.8 Hz, 4H), 7.05 – 6.96 (m, 2H), 4.07 (s, 2H), 1.36 (s, 36H). GN-2 (diethyl 10-(5'-(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H- xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-3,3'',5,5''-tetra-tert-butyl- [1,1':3',1''-terphenyl]-2'-yl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2- c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylate): A 250 mL 2N round bottom flask was charged with a stir bar and fitted with a finned condenser / gas adapter and flow control. The system was flushed with argon. To the flask was added GN-2.4 (1.000 mmol, 1.326 g), ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (2.100 mmol, 351 mg), and dry DCE (100 mL). The reaction mixture was stirred vigorously at room temperature for 30 seconds, then pTsOH.H2O (0.2000 mmol, 38 mg) was added. The reaction mixture was stirred under argon at room temperature for 19 hours, then DDQ was added (1.300 mmol, 295 mg), followed by dry DCE (5 mL). The mixture was stirred for 30 minutes at room temperature, then more DDQ (0.5000 mmol, 114 mg) was added, followed by dry DCE (5 mL). After stirring for another 30 minutes, the oxidation was complete. To the reaction was added Et3N (8.000 mmol, 1.1 mL) and BF3.OEt2(12.00 mmol, 1.5 mL). After 1 minute, the addition of Et3N (8.000 mmol, 1.1 mL) and BF3.OEt2(12.00 mmol, 1.5 mL) was repeated. The reaction mixture was stirred at 50 °C for 50 minutes, then the reaction mixture was evaporated onto 25g of flash silica gel in vacuo (bath = 60 ° C) and this silica placed in a loader and purified by flash chromatography on silica gel (330 g, equilibrate 0% acetone / hexanes, eluting 0% (2 CV) → 20% acetone / hexanes (15 CV)). Fractions containing product were evaporated to dryness in vacuo and repurified by loading directly onto a 220g column using 10% DCM / hexanes (dry load), eluting 0% EtOAc / DCM (2 CV) → 0.2% EtOAc / DCM (2 CV)→ isocratic 0.2% EtOAc / DCM. Fractions containing product were evaporated to dryness in vacuo to give an orange solid, 870 mg (52% yield). MS (APCI): calculated for Chemical Formula: C95H84BF14N3O9(M+H) = 1689; found: 1689. 1H NMR (400 MHz, TCE) δ 8.75 (s, 1H), 8.50 (s, 1H), 8.26 (s, 2H), 8.07 (s, 1H), 8.02 (s, 3H), 7.66 (d, J = 8.3 Hz, 2H), 7.53 – 7.44 (m, 1H), 7.43 – 7.34 (m, 4H), 7.27 (d, J = 8.1 Hz, 1H), 7.21 (t, J = 1.8 Hz, 2H), 7.04 – 6.91 (m, 6H), 4.24 (q, J = 7.1 Hz, 4H), 4.10 (s, 2H), 2.62 (s, 6H), 2.00 (s, 6H), 1.30 (t, J = 7.1 Hz, 6H), 1.12 (s, 36H). Synthesis procedure for GN-3 Compound GN-3.2 (diethyl 10-(4-acetoxy-2,6-dimethylphenyl)-5,5-difluoro-1,3,7,9- tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8- dicarboxylate): Compound GN-3.1 (17.75 mmol, 3412 mg), ethyl 2,4-dimethyl-1H- pyrrole-3-carboxylate (35.50 mmol, 5936 mg), and pTsOH.H2O (1.775 mmol, 338 mg) were stirred in dry DCE (100 mL) under argon at 40 °C for 90 minutes. The mixture was cooled to room temperature and DDQ (26.63 mmol, 6044 mg) was added, followed by stirring for 10 minutes. Et3N (71.01 mmol, 9.90 mL) and BF3.OEt2(106.5 mmol, 13.1 mL) were added to the reaction. The addition of Et3N (71.01 mmol, 9.90 mL), and BF3.OEt2(106.5 mmol, 13.1 mL) was repeated and the reaction was stirred at 50 °C for 30 minutes. The reaction mixture was cooled to room temperature and quenched with 50 mL of water and stirred for 5 minutes. The reaction mixture was filtered through a polypropylene frit to retain water. The frit was eluted with DCM. The organic eluent was evaporated onto 50g of flash silica gel in vacuo and packed into a loader. It was purified by flash chromatography on silica gel (330g, 0% EtOAc / DCM (2 CV) → 10% (5 CV), stopping gradient at 4.0%, then 6.2%). Fractions containing product were evaporated to dryness in vacuo, triturated with hot MeOH, adding water while hot to ~50%, cooled to room temperature, and then the precipitate was filtered off, washing with 50% MeOH / water. The product was dried in vacuo to give an orange solid, 6528 mg (66% yield). MS (APCI): calculated for Chemical Formula: C29H33BF2N2O6(M-H) = 555 found: 555.1H NMR (400 MHz, TCE) δ 6.99 (s, 2H), 4.28 (q, J = 7.1 Hz, 4H), 2.84 (s, 6H), 2.14 (s, 6H), 1.72 (s, 6H), 1.34 (t, J = 7.1 Hz, 6H). Compound GNC-3 : Compound GN-3 (diethyl 10-(4-acetoxy-2,6-dimethylphenyl)-1,3,7,9-tetramethyl- 5,5-bis(2,2,2-trifluoroacetoxy)-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'- f][1,3,2]diazaborinine-2,8-dicarboxylate): Compound GN-3.2 (0.5000 mmol, 277 mg) and trimethylsilyl 2,2,2-trifluoroacetate (5.000 mmol, 0.86 mL) were stirred in dry DCE (10 mL) at room temperature under argon. The reaction mixture was treated with BF3.OEt2(0.7500 mmol, 0.093 mL) and stirred at room temperature for 1 minute, then heated to 45 °C for 3 hours. The reaction mixture was cooled to room temperature and poured into ~30 mL of saturated sodium bicarbonate solution and stirred for 5 minutes. The reaction mixture was filtered through a polypropylene frit to retain water, eluting DCM. The reaction mixture was evaporated to dryness in vacuo, diluted with a small amount of DCM, and loaded onto ~40g of flash silica gel packed into a loader. It was purified by flash chromatography on silica gel (120g, 0% acetone / DCM (2 CV) → 25% (5 CV), stopping gradient at 0.9%, 1.5%, 1.9%, and 2.0%, isocratic at each step. Fractions containing product were evaporated to dryness in vacuo to give an orange solid, 198 mg (53% yield). MS (APCI): calculated for Chemical Formula: C33H33BF6N2O10(M-H) = 743 found: 743. Synthesis procedure for GN-4

[0051] Compound GN-4.1 (9-(3,5-bis(trifluoromethyl)phenyl)anthracene): 9- bromoanthracene (30.00 mmol, 7713 mg), (3,5-bis(trifluoromethyl)phenyl)boronic acid (60.00 mmol, 15474 mg), potassium carbonate (90.00 mmol, 12439 mg), and Pd(dppf)Cl2(1.500 mmol, 1098 mg) were stirred in dry THF (120 mL) and water (20 mL) under argon at 80 °C for 30 minutes, then cooled to room temperature. The THF was evaporated in vacuo, and the mixture was diluted with DCM, filtered through a polypropylene frit to retain water, eluting DCM, to the DCM added ~45g of flash silica gel, the DCM evaporated to dryness in vacuo, the silica packed into a loader, and purified by flash chromatography on silica gel (330g, 0% DCM / hexanes (2 CV) → 25% (10 CV)). Fractions containing product were evaporated to dryness in vacuo to give a light yellow solid, 11166 mg (95% yield). MS (APCI): calculated for Chemical Formula: C22H12F6(M+H) 391; found: 391.1H NMR (400 MHz, TCE) δ 8.62 (s, 1H), 8.13 (d, J = 1.1 Hz, 1H), 8.12 – 8.09 (m, 2H), 7.96 (d, J = 1.7 Hz, 2H), 7.60 – 7.39 (m, 6H). Compound GN-4.2 (9-(3,5-bis(trifluoromethyl)phenyl)-10-bromoanthracene): Compound GN-4.1 (28.60 mmol, 11165 mg), NBS (34.32 mmol, 6110 mg), and dry DCE (150 mL) were stirred at room temperature under argon for 90 minutes, then heated to 50 °C for 30 minutes. The reaction mixture was cooled to room temperature, the DCE evaporated in vacuo (water bath at RT), and the resulting solids washed with water. The residue was taken up into methanol, stirred for ~10 minutes, then filtered off, washing with MeOH. It was dried by suction to give a light yellow solid, 8082 mg (60% yield). MS (APCI): calculated for Chemical Formula: C22H11BrF6(M+H) 469; found: 469.1H NMR (400 MHz, TCE) δ 8.66 (dt, J = 8.9, 1.0 Hz, 2H), 8.12 (s, 1H), 7.93 (d, J = 1.7 Hz, 2H), 7.67 (ddd, J = 9.0, 6.1, 1.6 Hz, 2H), 7.55 – 7.41 (m, 4H). Compound GN-4.3 ((4-(10-(3,5-bis(trifluoromethyl)phenyl)anthracen-9-yl)-2,6- difluorophenyl)methanol): Compound GN-4.2 (6.000 mmol, 2815 mg), (3,5-difluoro-4- (hydroxymethyl)phenyl)boronic acid (9.000 mmol, 1691 mg), potassium carbonate (18.00 mmol, 2488 mg), and Pd(dppf)Cl2(0.3000 mmol, 220 mg) were stirred in dry THF (120 mL) and water (20 mL) under argon at 80 °C for 30 minutes, then cooled to room temperature. The THF was evaporated in vacuo, DCM was added, and the mixture filtered through a polypropylene frit to retain water, eluting DCM, ~45g of flash silica gel was added to the DCM, and the DCM evaporated to dryness in vacuo and packed into a loader. It was purified by flash chromatography on silica gel (220g, 0% EtOAc / DCM (2 CV) → 25% (10 CV)). Fractions containing product were evaporated to dryness in vacuo to gives a light yellow solid, 3014 mg (94% yield). MS (APCI): calculated for Chemical Formula: C29H16F8O (M+H) 533; found: 533.1H NMR (400 MHz, DMSO) δ 8.39 (td, J = 1.8, 0.9 Hz, 1H), 8.25 – 8.16 (m, 2H), 7.67 – 7.61 (m, 2H), 7.56 – 7.49 (m, 4H), 7.49 – 7.43 (m, 2H), 7.27 – 7.18 (m, 2H), 5.44 (t, J = 5.6 Hz, 1H), 4.70 (d, J = 5.7 Hz, 2H). Compound GN-4.4 (9-(3,5-bis(trifluoromethyl)phenyl)-10-(4-(chloromethyl)-3,5- difluorophenyl)anthracene): Compound GN-4.3 (5.601 mmol, 3014 mg) and 2-chloro- 1,3-dimethylimidazolium hexafluorophosphate (7.359 mmol, 2050 mg) were stirred in dry DMF (30 mL) under argon at 100 °C for 30 minutes, then cooled to room temperature. The reaction was diluted with water (~300 mL) to precipitate the product, the product filtered off, washing with water, the damp precipitate dissolved in DCM, filtered through polypropylene to retain water, eluting DCM, to the DCM was added ~45g of flash silica gel, the DCM evaporated to dryness in vacuo, the silica packed into a loader, and purified by flash chromatography on silica gel (220g, 100% DCM isocratic). Fractions containing product were evaporated to dryness in vacuo to give a light yellow solid, 3039 mg (98% yield). MS (APCI): calculated for Chemical Formula: C29H15ClF8(M+H) 551; found: 551.1H NMR (400 MHz, DMSO) δ 8.40 (tt, J = 1.8, 0.9 Hz, 1H), 8.21 (d, J = 1.7 Hz, 2H), 7.68 – 7.59 (m, 2H), 7.58 – 7.50 (m, 4H), 7.49 – 7.43 (m, 2H), 7.39 – 7.30 (m, 2H), 4.98 (s, 2H). Compound GN-4.5 (4-(10-(3,5-bis(trifluoromethyl)phenyl)anthracen-9-yl)-2,6- difluorobenzyl 2-isopropyl-4-methyl-1H-pyrrole-3-carboxylate): Compound GN-4.4 (2.413 mmol, 13298 mg), 2-isopropyl-4-methyl-1H-pyrrole-3-carboxylic acid (WuXi AppTech, 3.619 mmol, 605 mg), and potassium carbonate (4.825 mmol, 667 mg) were stirred in dry DMF (25 mL) at 100 °C under argon for 30 minutes, then cooled to room temperature. The product was precipitated by adding water (~300 mL), the product filtered off, washed with water, dissolved in DCM, filtered through polypropylene to retain water, eluting DCM, add ~45g of flash silica gel to the DCM, the DCM evaporated in vacuo, the silica gel packed into a loader, and purified by flash chromatography on silica gel (120g, 0% EtOAc / DCM (2 CV) → 5% (15 CV)). Fractions containing product were evaporated to dryness in vacuo to give a light yellow solid, 1549 mg (94% yield). MS (APCI): calculated for Chemical Formula: C38H27F8NO2(M+H) 682; found: 682.1H NMR (400 MHz, DMSO) δ 10.90 (s, 1H), 8.43 – 8.29 (m, 1H), 8.27 – 8.15 (m, 2H), 7.64 – 7.58 (m, 2H), 7.56 – 7.49 (m, 4H), 7.49 – 7.43 (m, 2H), 7.32 (d, J = 7.4 Hz, 2H), 6.54 – 6.37 (m, 1H), 5.45 (s, 2H), 3.70 (p, J = 7.1 Hz, 1H), 2.15 (d, J = 1.1 Hz, 3H), 1.19 (d, J = 7.0 Hz, 6H). Compound GN-4.6 (bis(4-(10-(3,5-bis(trifluoromethyl)phenyl)anthracen-9-yl)-2,6- difluorobenzyl) 10-(4-acetoxy-2,6-dimethylphenyl)-5,5-difluoro-3,7-diisopropyl-1,9- dimethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylate): Compound GN-4.5 (2.271 mmol, 1548 mg), Compound 1714-03 (1.136 mmol, 218 mg), and pTsOH.H2O (0.2271 mmol, 43 mg) were stirred in dry DCE (25 mL) at 65 °C for 90 minutes. The reaction was cooled to room temperature and treated with DDQ (1.703 mmol, 387 mg), then stirred at room temperature for 10 minutes, at which point the oxidation was done, and then treated with triethylamine (9.084 mmol, 1.3 mL) and BF3.OEt2(13.63 mmol, 1.7 mL). The triethylamine (9.084 mmol, 1.3 mL), and BF3.OEt2(13.63 mmol, 1.7 mL) were repeated, and the mixture heated to 65 °C for 30 minutes. The reaction mixture was cooled to room temperature, quenched with 30 mL of saturated sodium bicarbonate solution, stirred for ~10 minutes, filtered through a polypropylene frit to retain water, eluting DCM, the DCM was evaporated to dryness, the residue taken up in a small volume of DCM, loaded onto ~45g of flash silica gel packed into a loader, and purified by flash chromatography on silica gel (120g, 0% EtOAc / hexanes (2 CV) → 20% (10 CV), stopping at 8.0%, isocratic). Fractions containing product were evaporated to dryness in vacuo to give an orange solid, 1093 mg (61% yield). MS (APCI): calculated for Chemical Formula: C87H61BF18N2O6(M+H) 1583; found: 1583.1H NMR (400 MHz, TCE) δ 8.13 (d, J = 1.7 Hz, 2H), 8.03 – 7.97 (m, 4H), 7.71 – 7.60 (m, 4H), 7.54 – 7.48 (m, 4H), 7.46 (dt, J = 6.9, 3.2 Hz, 8H), 7.14 (d, J = 7.3 Hz, 4H), 7.03 (s, 2H), 5.57 (s, 4H), 3.91 (h, J = 7.1 Hz, 2H), 2.32 (s, 3H), 2.22 (s, 6H), 1.64 (s, 6H), 1.46 (d, J = 7.0 Hz, 12H). GN-4 (bis(4-(10-(3,5-bis(trifluoromethyl)phenyl)anthracen-9-yl)-2,6-difluorobenzyl) 10-(4-acetoxy-2,6-dimethylphenyl)-3,7-diisopropyl-1,9-dimethyl-5,5-bis(2,2,2- trifluoroacetoxy)-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8- dicarboxylate): Compound GN-4.6 (0.3449 mmol, 546 mg), TFAOTMS (6.897 mmol, 1.2 mL), and BF3.OEt2(1.379 mmol, 0.17 mL) were stirred in dry DCE (10 mL) at 45 ° C under argon for two hours. The mixture was cooled to room temperature and quenched with saturated sodium bicarbonate solution (40 mL), stirred for 10 minutes, and filtered through a polypropylene frit to retain water with eluting DCM. The DCM was evaporated in vacuo, the residue taken up in a small amount of DCM, loaded onto ~40g of flash silica gel in a loader, and purified by flash chromatography on silica gel (120g, 0% EtOAc / hexanes (2 CV) → 10% (10 CV), stop at 8.1%, 8.5%, isocratic at each step). Fractions containing product were evaporated to dryness, and the residue was triturated with methanol, filtered off the ppt, and dried in vacuo to give an orange solid, 275 mg (45% yield). MS (APCI): calculated for Chemical Formula: C91H61BF22N2O10(M+H) 1771; found: 1771. 1H NMR (400 MHz, TCE) δ 8.13 (s, 2H), 8.00 (d, J = 1.5 Hz, 4H), 7.65 (dt, J = 6.2, 3.2 Hz, 4H), 7.54 – 7.48 (m, 4H), 7.46 (dt, J = 6.9, 3.2 Hz, 8H), 7.13 (d, J = 7.2 Hz, 4H), 7.06 (s, 2H), 5.55 (s, 4H), 3.72 (p, J = 7.0 Hz, 2H), 2.31 (s, 3H), 2.29 (s, 6H), 1.67 (s, 6H), 1.37 (d, J = 7.0 Hz, 12H).

[0052] Synthesis procedure for GN-5 Compound GN-5.1 (5,6,8-tribromo-1H,3H-benzo[de]isochromene-1,3-dione): 6- bromo-1H,3H-benzo[de]isochromene-1,3-dione (50.00 mmol, 13.855 g) and NBS (160.0 mmol, 28.840g) were mixed dry under argon, then suspended in 96% sulfuric acid (100 mL) and heated to 60 °C with stirring for 30 minutes. The reaction mixture was cooled to room temperature and carefully added to a slurry of crushed ice and water with vigorous stirring. The suspension was stirred until all ice had melted, then the resulting precipitate was filtered off, washing with water. The material was dried by suction, then in a vacuum oven at 100 °C overnight to give a tan solid, mixture of tri-and tetra-bromo (too insoluble for NMR). MS (APCI): calculated for Chemical Formula: C12H3Br3O3(M+H) 433; found: 433. Used as-is in the next step. Compound GN-5.2 (2-((tert-butoxycarbonyl)amino)ethyl 2-isopropyl-4-methyl-1H- pyrrole-3-carboxylate): 2-isopropyl-4-methyl-1H-pyrrole-3-carboxylic acid (WuXi AppTech, 20.00 mmol, 3344 mg), tert-butyl (2-hydroxyethyl)carbamate (100.0 mmol, 15.5 mL), and DMAP (30.00 mmol, 3666 mg) were stirred in dry DMF (35 mL) and pre-heated to 100 °C with stirring under argon. To the reaction was added EDC.HCl (50.00 mmol, 9585 mg), washing down with 15 mL dry DMF. The mixture was stirred under argon at 100 °C for 45 minutes, then cooled to room temperature. As much DMF as possible was removed in vacuo, then the remainder was loaded onto ~40g of flash silica gel packed into a loader and purified by flash chromatography on silica gel (220g, 0% EtOAc / hexanes (2 CV) → 40% (10 CV)). Fractions containing product were evaporated to dryness in vacuo to give a thick, light-yellow oil, 4416 mg (71% yield). MS (APCI): calculated for Chemical Formula: C16H26N2O4(M+H) 311; found: 311.1H NMR (400 MHz, TCE) δ 8.23 (s, 1H), 6.42 (dd, J = 2.3, 1.2 Hz, 1H), 4.85 (t, J = 6.0 Hz, 1H), 4.25 (t, J = 5.4 Hz, 2H), 3.72 (p, J = 7.0 Hz, 1H), 3.46 (q, J = 5.7 Hz, 2H), 2.22 (d, J = 1.1 Hz, 3H), 1.43 (s, 9H), 1.25 (d, J = 7.0 Hz, 6H). Compound GN-5.3 (2-((2-isopropyl-4-methyl-1H-pyrrole-3-carbonyl)oxy)ethan-1- aminium 2,2,2-trifluoroacetate): Compound GN-5.2 (14.22 mmol, 4416 mg) was dissolved in 1:1 TFA:DCM (30 mL) and stirred at room temperature for 30 minutes, then as much TFA as possible was removed in vacuo with a bath temperature of 40 °C to give a reddish oil. It was then used as-is in the next step. MS (APCI): calculated for Chemical Formula: C11H18N2O2(M+H) 211; found: 211. Compound GN-5.4 (2-(5,6,8-tribromo-1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)- yl)ethyl 2-isopropyl-4-methyl-1H-pyrrole-3-carboxylate): Compound GN-5.3 (14.22 mmol, 2992 mg), Compound GN-5.1 (9.485 mmol, 4125 mg), and DMAP (2.845 mmol, 348 mg) were stirred in dry DMF (50 mL) at 90 °C under argon for 60 minutes, then cooled to 0 °C and the mixture acidified to pH ~1 with 12N HCl. The mixture was diluted with water (250 mL) and the resulting precipitate was stirred for 10 minutes, the precipitate filtered off, washing with water, 1:1 MeOH:water, dried by suction, then used as-is (damp) in the next step. Not soluble enough for NMR. MS (APCI): calculated for Chemical Formula: C23H19Br3N2O4(M+H) 625; found: 625. Compound GN-5.5 (2-(1,3-dioxo-5,6,8-tris(4-(trifluoromethyl)phenyl)-1H- benzo[de]isoquinolin-2(3H)-yl)ethyl 2-isopropyl-4-methyl-1H-pyrrole-3- carboxylate): Compound GN-5.4 (crude, damp, assume 100%, 10.33 mmol, 6478 mg), (4-(trifluoromethyl)phenyl)boronic acid (82.64 mmol, 15.693 g), potassium carbonate (61.98 mmol, 8566 mg), and Pd(dppf)Cl2(1.550 mmol, 1134 mg) were stirred in dry THF (120 mL) and water (30 mL) at 80 °C under argon for 90 minutes, then cooled to room temperature. Most of the THF was removed in vacuo, and DCM was added, acidified with 12N HCl to pH ~1, filtered through a polypropylene frit to retain water, eluting with DCM, evaporated the DCM eluent in vacuo, dissolved in a small volume of DCM, loaded onto ~40g of flash silica gel packed into a loader, and purified by flash chromatography on silica gel (220g, 0% EtOAc / tol (2 CV) → 5% (10 CV), stop at 2.5%, isocratic). Fractions containing product were evaporated to dryness in vacuo to give a yellow solid, 2364 mg (28% yield from mono-Br). MS (APCI): calculated for Chemical Formula: C44H31F9N2O4(M+H) 823; found: 823.1H NMR (400 MHz, TCE) δ 8.89 (d, J = 1.7 Hz, 1H), 8.68 (s, 1H), 8.09 (d, J = 1.7 Hz, 1H), 8.07 (s, 1H), 7.77 (d, J = 8.3 Hz, 2H), 7.70 (dd, J = 8.3, 2.4 Hz, 4H), 7.55 (d, J = 8.1 Hz, 2H), 7.40 (d, J = 7.8 Hz, 2H), 7.28 (d, J = 8.0 Hz, 2H), 6.38 (dd, J = 2.3, 1.2 Hz, 1H), 4.65 (d, J = 5.3 Hz, 2H), 4.61 (d, J = 5.2 Hz, 2H), 3.71 (hept, J = 6.9 Hz, 1H), 2.16 (d, J = 1.0 Hz, 3H), 1.18 (d, J = 7.0 Hz, 6H). Compound GN-5.7 (bis(2-(1,3-dioxo-5,6,8-tris(4-(trifluoromethyl)phenyl)-1H- benzo[de]isoquinolin-2(3H)-yl)ethyl) 10-(4-acetoxy-2,6-dimethylphenyl)-5,5- difluoro-3,7-diisopropyl-1,9-dimethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'- f][1,3,2]diazaborinine-2,8-dicarboxylate): Compound GN-5.5 (2.565 mmol, 2110 mg), Compound GN-5.6 (1.282 mmol, 246 mg), and pTsOH.H2O (0.2565 mmol, 49 mg) were stirred in dry DCE (30 mL) at 60 °C under argon for 90 minutes, then cooled to room temperature. The reaction mixture was treated with DDQ (2.564 mmol, 582 mg), and stirred at room temperature for 10 minutes, at which point oxidation was done, and it was treated with triethylamine (10.26 mmol, 1.4 mL), and BF3.OEt2(15.39 mmol, 1.9 mL). The treatment with triethylamine (10.26 mmol, 1.4 mL), BF3.OEt2(15.39 mmol, 1.9 mL) was repeated, and the mixture heated to 60 ° C for 3 hours, then room temperature overnight. The reaction mixture was quenched with 30 mL saturated sodium bicarbonate solution, stirred for 10 minutes, then filtered through a polypropylene frit to retain water, eluting with DCM. The DCM was evaporated to dryness in vacuo, and the residue taken up in a small volume of toluene, loaded onto ~40g of flash silica gel packed into a loader, and purified by flash chromatography on silica gel (120g, 0% acetone / toluene (2 CV) → 5% (10 CV), stopping at 2.5%, isocratic). Fractions containing product were evaporated to dryness in vacuo to give an orange solid, 1253 mg (52% yield). MS (APCI): calculated for Chemical Formula: C99H69BF20N4O10(M+H) 1865; found: 1865.1H NMR (400 MHz, TCE) δ 8.85 (d, J = 1.7 Hz, 2H), 8.62 (s, 2H), 8.09 (d, J = 1.8 Hz, 2H), 7.76 (d, J = 8.2 Hz, 4H), 7.73 – 7.66 (m, 8H), 7.54 (d, J = 8.2 Hz, 4H), 7.40 (d, J = 7.9 Hz, 4H), 7.26 (d, J = 8.0 Hz, 4H), 6.85 (s, 2H), 4.63 (s, 8H), 3.78 (p, J = 7.0 Hz, 2H), 2.30 (s, 3H), 2.04 (s, 6H), 1.56 (s, 6H), 1.32 (d, J = 7.0 Hz, 12H). Compound GN-5 (bis(2-(1,3-dioxo-5,6,8-tris(4-(trifluoromethyl)phenyl)-1H- benzo[de]isoquinolin-2(3H)-yl)ethyl) 10-(4-acetoxy-2,6-dimethylphenyl)-5,5- dicyano-3,7-diisopropyl-1,9-dimethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'- f][1,3,2]diazaborinine-2,8-dicarboxylate): Compound GN-5.7 (0.5500 mmol, 1026 mg), TMSCN (5.500 mmol, 0.69 mL), and BCl3(0.5500 mmol, 0.55 mL) were stirred in dry DCE (15 mL) at 60 °C under argon for two hours, then cooled to room temperature and quenched with 30 mL of 6N HCl, stirred for 10 minutes, filtered through a polypropylene frit to retain water, eluting with DCM, the DCM evaporated to dryness in vacuo, the residue taken up in a small volume of toluene, loaded onto ~40g of flash silica gel packed into a loader, and purified by flash chromatography on silica gel (120g, 0% acetone / toluene (2 CV) → 5% (10 CV), stopping at 2.8%, then back to 2.6%, isocratic at each step). Fractions containing product and mono-F-mono-CN were collected and evaporated to dryness in vacuo. The mixture was re-submitted to the same reaction conditions, then quenched with 10% citric acid (30 mL) stirred for 10 minutes, filtered through a polypropylene frit to retain water, eluting with DCM, the DCM evaporated to dryness, dissolved in a small volume of DCM, loaded onto ~40g of flash silica gel packed into a loader, and purified by flash chromatography on silica gel (120g, same gradient as above). Fractions containing product were evaporated to dryness in vacuo to give an orange solid, 537 mg (52% yield). MS (APCI): calculated for Chemical Formula: C101H69BF18N6O10(M+H) 1879; found: 1879. 1H NMR (400 MHz, TCE) δ 8.85 (d, J = 1.8 Hz, 2H), 8.64 (s, 2H), 8.10 (d, J = 1.8 Hz, 2H), 7.77 (d, J = 8.2 Hz, 4H), 7.73 – 7.67 (m, 8H), 7.55 (d, J = 8.1 Hz, 4H), 7.41 (d, J = 7.9 Hz, 4H), 7.27 (d, J = 8.0 Hz, 4H), 6.87 (s, 2H), 4.65 (d, J = 5.8 Hz, 8H), 3.94 – 3.69 (m, 2H), 2.31 (s, 3H), 2.04 (s, 6H), 1.62 (s, 6H), 1.48 (d, J = 6.8 Hz, 12H).

[0053] Synthesis procedure for GN-6: Compound GN-6.1 (5,11-dibromo-2-(4-(hydroxymethyl)phenyl)-1H-xantheno[2,1,9- def]isoquinoline-1,3(2H)-dione): 5,11-dibromo-1H,3H-isochromeno[6,5,4- mna]xanthene-1,3-dione (WuXI, 6.000 mmol, 2676 mg), (4-aminophenyl)methanol (7.200 mmol, 887 mg), and DMAP (3.600 mmol, 440 mg) were stirred in dry DMF (25 mL) at 140 °C for 5 hours, then cooled in an ice-water batch and quenched with 6N HCl (~5 mL, to pH ~1), and diluted with water (~100 mL), filtered off ppt, washing with water. The crude product was dried in a vacuum oven overnight at 100 °C. Not very soluble, so used in the next step without further characterization or purification. Compound GN-6.2 (2-(4-(hydroxymethyl)phenyl)-5,11-bis(4- (trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione): Compound GN-6.1 (assume 100% yield, 6.000 mmol, 3307 mg), (4- (trifluoromethyl)phenyl)boronic acid (24.00 mmol, 4538 mg), potassium carbonate (24.00 mmol, 3317 mg), and Pd(dppf)Cl2(0.4200 mmol, 307 mg) were stirred in THF / DMF / water (50 mL / 8 mL / 2 mL) at 85 °C under argon for 30 minutes, then cooled to room temperature. The reaction mixture was cooled in an ice-water bath, diluted with water to precipitate the product, and the product was filtered off, washing with water. The damp precipitate was dissolved in DCM, dried over magnesium sulfate, filtered, and evaporated to dryness in vacuo. Dissolved in a small volume of DCM and evaporated onto ~45g of flash silica gel in vacuo and packed into a loader. Purified by flash chromatography on silica gel (120g, 0% acetone / DCM 2 CV) → 5% (5 CV), stop at 4.3%, 5.0%, isocratic at each step. Fractions containing product were evaporated to dryness in vacuo to give a yellow solid, 1980 mg (48% yield).1H NMR (400 MHz, TCE) δ 8.70 (s, 1H), 8.48 (s, 1H), 7.92 (d, J = 8.3 Hz, 2H), 7.89 – 7.82 (m, 4H), 7.68 (d, J = 8.0 Hz, 2H), 7.61 (d, J = 8.1 Hz, 2H), 7.43 (ddd, J = 8.5, 7.1, 1.5 Hz, 1H), 7.36 (d, J = 8.2 Hz, 2H), 7.31 (dd, J = 8.3, 1.3 Hz, 1H), 7.10 (dd, J = 8.3, 1.5 Hz, 1H), 6.96 (ddd, J = 8.4, 7.2, 1.4 Hz, 1H), 4.83 (s, 2H). MS (APCI): calculated for Chemical Formula: C39H21F6NO4(M+H) = 682; found: 682. Compound GN-6.3 (2-(4-(chloromethyl)phenyl)-5,11-bis(4-(trifluoromethyl)phenyl)- 1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione): Compound GN-6.12(1.000 mmol, 682 mg) and 2-chloro-1,3-dimethyl-1H-imidazol-3-ium hexafluorophosphate (2.000 mmol, 3341 mg) were heated in dry DMF (20 mL) under argon for 15h, then room temperature over the weekend. The crude product was precipitated by adding water, filtered off, washed with water, dissolved in DCM, dried over magnesium sulfate, filtered, and evaporated to dryness in vacuo. Dissolved in a small volume of DCM and evaporated onto ~45g of flash silica gel in vacuo and packed into a loader. Purified by flash chromatography (120g, 0% acetone / DCM (2 CV) → 10% (10 CV), stopping at 2.5%, 4.5%, and 10.0%, isocratic at each step). Fractions containing product were evaporated to dryness in vacuo to give a yellow solid, 540 mg, (62% yield).1H NMR (400 MHz, TCE) δ 8.71 (s, 1H), 8.48 (s, 1H), 7.91 (d, J = 8.3 Hz, 2H), 7.89 – 7.82 (m, 4H), 7.67 (d, J = 8.0 Hz, 2H), 7.66 – 7.60 (m, 2H), 7.43 (ddd, J = 8.5, 7.1, 1.5 Hz, 1H), 7.39 – 7.34 (m, 2H), 7.31 (dd, J = 8.3, 1.3 Hz, 1H), 7.10 (dd, J = 8.3, 1.5 Hz, 1H), 6.96 (ddd, J = 8.4, 7.1, 1.3 Hz, 1H), 4.73 (s, 2H). MS (APCI): calculated for Chemical Formula: C39H20ClF6NO3(M+H) = 700; found: 700. Compound GN-6.4 (4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H- xantheno[2,1,9-def]isoquinolin-2(3H)-yl)benzyl 2-isopropyl-4-methyl-1H-pyrrole-3- carboxylate): Compound GN-6.3 (0.7714 mmol, 540 mg), Compound 1725-31 (1.543 mmol, 258 mg), and K2CO3(1.928 mmol, 267 mg) were stirred in dry DMF (10 mL) at 100 °C under argon for three hours. The reaction mixture was cooled to room temperature, diluted with water, and the resulting precipitate collected by vacuum filtration, washing with water. The damp precipitate was dissolved in DCM, dried over magnesium sulfate, filtered, and evaporated to dryness. It was then dissolved in a small volume of DCM and loaded onto ~15g of flash silica gel packed into a loader and purified by flash chromatography on silica gel (120g, 0% acetone / DCM (2 CV) → 10% (10 CV), stopping at 3.0% and eluting isocratic). Fractions containing product were evaporated to dryness in vacuo to give a yellow solid, 561 mg (88% yield).1H NMR (400 MHz, TCE) δ 8.71 (s, 1H), 8.48 (s, 1H), 8.11 (s, 1H), 7.91 (d, J = 8.2 Hz, 2H), 7.89 – 7.81 (m, 4H), 7.67 (d, J = 8.1 Hz, 2H), 7.64 (d, J = 8.4 Hz, 2H), 7.42 (ddd, J = 8.5, 7.1, 1.5 Hz, 1H), 7.37 (d, J = 8.4 Hz, 2H), 7.31 (dd, J = 8.2, 1.3 Hz, 1H), 7.10 (dd, J = 8.4, 1.5 Hz, 1H), 6.96 (ddd, J = 8.4, 7.1, 1.4 Hz, 1H), 6.44 (dd, J = 2.4, 1.2 Hz, 1H), 5.43 (s, 2H), 3.83 (hept, J = 6.9 Hz, 1H), 2.30 (d, J = 1.0 Hz, 3H), 1.28 (d, J = 7.0 Hz, 6H). MS (APCI): calculated for Chemical Formula: C48H32F6N2O5(M+H) = 831; found: 831. Compound GN-6.5 (bis(4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H- xantheno[2,1,9-def]isoquinolin-2(3H)-yl)benzyl) 10-(4-acetoxy-2,6-dimethylphenyl)- 5,5-difluoro-3,7-diisopropyl-1,9-dimethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'- f][1,3,2]diazaborinine-2,8-dicarboxylate): Compound GN-6.4 (0.8414 mmol, 699 mg), Compound 1714-03 (0.4207 mmol, 81 mg), and pTsOH.H2O (0.04207 mmol, 8 mg) were stirred in dry DCE (20 mL) at room temperature for one hour, then heated to 60 °C for 90 minutes, then 70 °C for 30 minutes, then 85 °C for 12 hours, then room temperature. To the flask was added DDQ (0.8414 mmol, 191 mg), washing down with 5 mL DCE, and stirred for 15 minutes. Et3N (3.366 mmol, 0.47 mL), and BF3.OEt2(5.0487 mmol, 0.62 mL) were added to the reaction. The addition of Et3N (3.366 mmol, 0.47 mL), and BF3.OEt2(5.0487 mmol, 0.62 mL) was repeated and the reaction stirred at 70 °C for 60 minutes. The reaction mixture was cooled to room temperature and quenched with ~30 mL of saturated sodium bicarbonate solution and stirred for ten minutes. The mixture was filtered through a polypropylene frit to retain water, eluting with DCM. The DCM eluent was evaporated to dryness in vacuo, dissolved in a small volume of DCM, loaded onto ~40g of flash silica gel packed into a loader, and purified by flash chromatography on silica gel (120g, 0% acetone / DCM (2 CV) → 5% (10 CV), stopping at 0.3%, 0.5%, 0.7%, 1.0%, 1.3%, 1.7%, and 2.5%, isocratic at each step). Fractions containing product were evaporated to dryness in vacuo, triturated with methanol, dissolved in DCM, and evaporated to dryness in vacuo to give an orange solid, 438 mg (55% yield).1H NMR (400 MHz, TCE) δ 8.70 (s, 2H), 8.47 (s, 2H), 7.91 (d, J = 8.3 Hz, 4H), 7.89 – 7.79 (m, 8H), 7.67 (d, J = 8.0 Hz, 5H), 7.64 – 7.57 (m, 4H), 7.43 (ddd, J = 8.5, 7.1, 1.5 Hz, 2H), 7.39 – 7.34 (m, 4H), 7.31 (dd, J = 8.4, 1.4 Hz, 2H), 7.10 (dd, J = 8.4, 1.5 Hz, 2H), 7.02 – 6.91 (m, 4H), 5.40 (s, 4H), 3.90 (p, J = 7.0 Hz, 2H), 2.30 (s, 3H), 2.18 (s, 6H), 1.60 (s, 6H), 1.47 (d, J = 7.0 Hz, 12H). MS (APCI): calculated for Chemical Formula: C107H71BF14N4O12(M+H) = 1881; found: 1881. Compound GN-6 (bis(4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H- xantheno[2,1,9-def]isoquinolin-2(3H)-yl)benzyl) 10-(4-acetoxy-2,6-dimethylphenyl)- 5,5-dicyano-3,7-diisopropyl-1,9-dimethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'- f][1,3,2]diazaborinine-2,8-dicarboxylate): Compound GN-6.5 (0.1478 mmol, 278 mg) was dissolved in dry DCE (10 mL) and stirred under argon at room temperature. The reaction mixture was treated with TMSCN (2.955 mmol, 0.37 mL) and BF3.OEt2(0,.5910 mmol, 0.073 mL) and stirred at room temperature for a few minutes, then heated to 45 °C for two hours. The reaction mixture was cooled to room temperature and quenched with ~30 mL of saturated sodium bicarbonate solution and stirred rapidly at room temperature for about 10 minutes. The mixture was filtered through a polypropylene frit to retain water, eluting with DCM. The DCM was evaporated to dryness in vacuo, taken up in a small volume of DCM, and loaded onto ~15g of flash silica gel packed into a loader. It was purified by flash chromatography on silica gel (0% acetone / DCM (2 CV) → 10% (10 CV), stopping at 2.1%, then 3.3%, isocratic at each step). Fractions containing product were evaporated to dryness in vacuo, triturated with methanol, dissolved in DCM, and evaporated to dryness in vacuo to give an orange solid, 116 mg (41% yield). 1H NMR (400 MHz, DMSO) δ 8.53 (s, 2H), 8.26 (s, 2H), 8.06 (d, J = 8.1 Hz, 4H), 7.98 – 7.92 (m, 9H), 7.79 (d, J = 8.0 Hz, 4H), 7.60 (d, J = 8.1 Hz, 4H), 7.48 (dt, J = 8.6, 4.3 Hz, 2H), 7.38 (t, J = 8.8 Hz, 6H), 7.11 (s, 2H), 7.00 (d, J = 4.2 Hz, 4H), 5.43 (s, 4H), 3.76 (p, J = 6.9 Hz, 2H), 2.24 (s, 3H), 2.09 (s, 6H), 1.58 (s, 6H), 1.47 (d, J = 6.9 Hz, 12H). MS (APCI): calculated for Chemical Formula: C109H71BF12N6O12(M+H) = 1896; found: 1896.

[0054] Synthesis procedure for GN-7 Compound GN-7.1 (5,6,8-tribromo-1H,3H-benzo[de]isochromene-1,3-dione): 6- bromo-1H,3H-benzo[de]isochromene-1,3-dione (50.00 mmol, 13.855 g) and NBS (160.0 mmol, 28.840g) were mixed dry under argon, then suspended in 96% sulfuric acid (100 mL) and heated to 60 °C with stirring for 30 minutes. The reaction mixture was cooled to room temperature and carefully added to a slurry of crushed ice and water with vigorous stirring. The suspension was stirred until all ice had melted, then the resulting precipitate was filtered off, washing with water. The material was dried by suction, then in a vacuum oven at 100 °C overnight to give a tan, solid mixture of tri-and tetra-bromo (too insoluble for NMR). MS (APCI): calculated for Chemical Formula: C12H3Br3O3(M+H) 433; found: 433. Used as-is in the next step. Compound GN-7.2 (5,6,8-tribromo-2-(3-hydroxypropyl)-1H-benzo[de]isoquinoline- 1,3(2H)-dione): Compound GN-7.1 (assume 100%, 50.00 mmol, 21744 mg), 3- aminopropan-1-ol (100.0 mmol, 7.6 mL), and DMAP (15.00 mmol, 1833 mg) were stirred in dry DMF (100 mL) at 70 °C under argon for 30 minutes, then heated to 110 °C for another 40 minutes. The reaction mixture was cooled to room temperature and poured into ~500 mL of stirred water, then diluted to ~900 mL total volume with more water. The precipitate was filtered off, washing water. The product was dried by suction, then in a vacuum oven at 80 °C overnight to give a tan powder, assume 100% (too insoluble for NMR). MS (APCI): calculated for Chemical Formula: C15H10Br3NO3(M+H) 490; found: 490. Used as-is in the next step. Compound GN-7.3 (5,6,8-tris(3,5-bis(trifluoromethyl)phenyl)-2-(3-hydroxypropyl)- 1H-benzo[de]isoquinoline-1,3(2H)-dione): Compound GN-7.12 (10.00 mmol, 4920 mg, assume 100% yield), (3,5-bis(trifluoromethyl)phenyl)boronic acid (60.00 mmol, 15474 mg), potassium carbonate (80.00 mmol, 11057 mg), and Pd(dppf)Cl2(1.500 mmol, 1098 mg) were stirred in dry THF (120 mL) and water (30 mL) under argon at 80 °C for 210 minutes, then cooled to room temperature. The reaction mixture was acidified with TFA to pH ~2, the THF evaporated in vacuo, the residue dissolved in DCM, the mixture filtered through a polypropylene frit to retain water, eluting DCM, added ~45g of flash silica gel to the DCM, evaporated the DCM to dryness, packed the silica gel into a loader, and purified by flash chromatography on silica gel (220g, 0% EtOAc / DCM (2 CV) → 10% (10 CV)). Fractions containing product were evaporated to dryness in vacuo to give a tannish solid, 2361 mg (26% yield from mono-Br-anhydride). MS (APCI): calculated for Chemical Formula: C39H19F18NO3(M+H) 892; found: 892.1H NMR (400 MHz, DMSO) δ 8.90 (d, J = 1.7 Hz, 1H), 8.70 (s, 1H), 8.34 (d, J = 1.6 Hz, 2H), 8.30 (d, J = 1.8 Hz, 1H), 8.16 (s, 1H), 8.12 (s, 3H), 8.02 (s, 1H), 7.92 (d, J = 1.7 Hz, 2H), 4.18 (dd, J = 8.4, 6.2 Hz, 2H), 3.53 (t, J = 6.3 Hz, 2H), 1.85 (p, J = 6.5 Hz, 2H). Compound GN-7.4 (5,6,8-tris(3,5-bis(trifluoromethyl)phenyl)-2-(3-chloropropyl)-1H- benzo[de]isoquinoline-1,3(2H)-dione): Compound GN-7.3 (9.409 mmol, 8389 mg), and 2-chloro-1,3-dimethylimidazolium hexafluorophosphate (12.23 mmol, 3408 mg) were heated in dry DMF (50 mL) at 100 °C under argon overnight. The reaction was cooled to room temperature and as much DMF as possible was removed in vacuo. The residue was diluted with DCM, loaded onto a loader packed with ~45g of flash silica gel, and purified by flash chromatography on silica gel (220g, 70% DCM / hexanes (2 CV) → 100% (10 CV)). Fractions containing product were evaporated to dryness in vacuo to give a tannish solid, 7755 mg (81% yield). MS (APCI): calculated for Chemical Formula: C39H18ClF18NO2(M+H) 910; found: 910. The reaction was stopped too early, so there was a mixture of -OH and -Cl. It was used in the next step as-is. Compound GN-7.5 (2-(5,6,8-tris(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H- benzo[de]isoquinolin-2(3H)-yl)ethyl 2-isopropyl-4-methyl-1H-pyrrole-3- carboxylate): Compound GN-7.4 (3.000 mmol, 2730 mg), 2-isopropyl-4-methyl-1H- pyrrole-3-carboxylic acid (WuXi AppTech, 4.500 mmol, 752 mg), and potassium carbonate (6.000 mmol, 829 mg) were stirred in dry DMF (25 mL) at 100 °C under argon for 180 minutes, then cooled to room temperature. As much DMF as possible was removed in vacuo, the residue partitioned with DCM:water, filtered through a polypropylene frit to retain water, eluting DCM, added ~45g of flash silica gel to the DCM, evaporated to dryness, packed into a loader, and purified by flash chromatography on silica gel (120g, 0% acetone / DCM (2 CV) → 10% (15 CV)). Fractions containing product were evaporated to dryness in vacuo to give a tannish solid, 2993 mg (96% yield). MS (APCI): calculated for Chemical Formula: C47H28F18N2O4(M+H) 1027 found: 1027.1H NMR (400 MHz, DMSO) δ 10.87 – 10.60 (m, 1H), 8.94 (d, J = 1.7 Hz, 1H), 8.70 (s, 1H), 8.37 (d, J = 1.6 Hz, 2H), 8.32 (d, J = 1.8 Hz, 1H), 8.17 (s, 1H), 8.11 (d, J = 3.1 Hz, 3H), 8.03 (s, 1H), 7.91 (d, J = 1.7 Hz, 2H), 6.43 – 6.26 (m, 1H), 4.31 (t, J = 7.1 Hz, 2H), 4.23 (t, J = 6.1 Hz, 2H), 3.69 (p, J = 7.0 Hz, 1H), 2.21 – 2.03 (m, 5H), 1.16 (s, 6H). Compound GN-7.7 (bis(3-(5,6,8-tris(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H- benzo[de]isoquinolin-2(3H)-yl)propyl) 10-(4-acetoxy-2,6-dimethylphenyl)-5,5- difluoro-3,7-diisopropyl-1,9-dimethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'- f][1,3,2]diazaborinine-2,8-dicarboxylate): Compound GN-7.5 (2.876 mmol, 2993 mg), Compound GN-7.6 (1.438 mmol, 276 mg), and pTsOH.H2O (0.2876 mmol, 55 mg) were stirred in dry DCE (35 mL) at 65 °C under argon for 60 minutes, then cooled to room temperature. The reaction mixture was treated with DDQ (4.314 mmol, 979 mg), stirred at room temperature for 10 minutes, at which point oxidation was done, and treated with triethylamine (11.50 mmol, 1.6 mL), BF3.OEt2(17.25 mmol, 2.1 mL). The triethylamine (11.50 mmol, 1.6 mL), BF3.OEt2(17.25 mmol, 2.1 mL) treatment was repeated, and the mixture heated to 65 °C for 3 hours, then room temperature overnight. The reaction mixture was quenched with 40 mL saturated sodium bicarbonate solution, stirred for 10 minutes, then filtered through a polypropylene frit to retain water, eluting with DCM. The DCM was evaporated to dryness in vacuo, the residue taken up in a small volume of DCM, loaded onto ~45g of flash silica gel packed into a loader, and purified by flash chromatography on silica gel (220g, 0% acetone / DCM (2 CV) → 10% (10 CV), stop at 2.2%, 3.0%, isocratic at each step). Fractions containing product were evaporated to dryness in vacuo, dissolved in toluene, loaded onto ~40g of flash silica gel packed into a loader, and purified again by flash chromatography on silica gel (120g, 0% EtOAc / toluene (2 CV) → 10% (10 CV), stop at 3.2%, isocratic). Fractions containing product were evaporated to dryness in vacuo, triturated with a small volume of hot toluene, cooled to room temperature, filtered off, washed with a small volume of toluene, and dried in vacuo at 100 °C to give an orange solid, 2239 mg (68% yield). Too big for LCMS.1H NMR (400 MHz, TCE) δ 8.95 (d, J = 1.8 Hz, 2H), 8.78 (s, 2H), 8.13 (d, J = 1.8 Hz, 2H), 8.03 (d, J = 1.6 Hz, 4H), 7.96 (s, 4H), 7.83 (s, 2H), 7.72 (d, J = 1.6 Hz, 4H), 7.58 (d, J = 1.6 Hz, 4H), 6.96 (s, 2H), 4.40 (q, J = 6.1 Hz, 8H), 3.89 (p, J = 7.1 Hz, 2H), 2.39 – 2.22 (m, 5H), 2.17 (s, 6H), 1.46 (d, J = 7.0 Hz, 12H). Compound GN-7 (bis(3-(5,6,8-tris(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H- benzo[de]isoquinolin-2(3H)-yl)propyl) 10-(4-acetoxy-2,6-dimethylphenyl)-5,5- dicyano-3,7-diisopropyl-1,9-dimethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'- f][1,3,2]diazaborinine-2,8-dicarboxylate): Compound GN-7.7 (0.4006 mmol, 922 mg), TMSCN (8.012 mmol, 1.0 mL), and BF3.OEt2(1.602 mmol, 0.20 mL) were stirred in dry DCE (10 mL) at 50 °C 60 minutes, then cooled to room temperature and quenched with 30 mL of saturated sodium bicarbonate solution, stirred for 10 minutes, filtered through a polypropylene frit to retain water, eluting with DCM, the DCM evaporated to dryness in vacuo, the residue dissolved in a small volume of DCM and loaded onto ~40g of flash silica gel packed into a loader, and purified by flash chromatography on silica gel (120g, 0% EtOAc / hexanes (2 CV) → 25% (10 CV), stop at 19.6%, isocratic). Fractions containing product were evaporated to dryness in vacuo to give an orange solid, 495 mg (53% yield). Too big for LCMS.1H NMR (400 MHz, TCE) δ 8.94 (d, J = 1.7 Hz, 2H), 8.78 (s, 2H), 8.13 (d, J = 1.7 Hz, 2H), 8.03 (s, 4H), 7.96 (s, 4H), 7.83 (s, 2H), 7.76 – 7.70 (m, 4H), 7.60 – 7.55 (m, 4H), 6.99 (s, 2H), 4.53 – 4.34 (m, 8H), 3.87 (p, J = 6.8 Hz, 2H), 2.35 – 2.22 (m, 7H), 2.14 (s, 6H), 1.65 (s, 6H), 1.57 (d, J = 6.9 Hz, 12H). Synthesis procedure for GN-8 Compound GN-8.2 (5,6,8-tribromo-2-(3-hydroxypropyl)-1H-benzo[de]isoquinoline- 1,3(2H)-dione): Compound GN-8.1 (17.37 mmol, 7555 mg), 3-aminopropan-1-ol (26.06 mmol, 2.0 mL), and DMAP (5.212 mmol, 637 mg) were stirred in dry DMF (50 mL) at 50 °C under argon for 30 minutes, then heated to 110 °C for another 30 minutes. The reaction mixture was cooled to 0 °C and quenched with 12N HCl to pH ~1, then diluted with water (~500 mL total volume). The precipitate was filtered off, washing with water. The product was dried by suction overnight to give a tan powder, assume 100%, (too insoluble for NMR). MS (APCI): calculated for Chemical Formula: C15H10Br3NO3(M+H) 490; found: 490. It was used as-is in the next step. Compound GN-8.3 (2-(3-hydroxypropyl)-5,6,8-tris(4-(trifluoromethyl)phenyl)-1H- benzo[de]isoquinoline-1,3(2H)-dione): Compound GN-8.2 (assume 100% yield, 17.37 mmol, 8547 mg), (4-(trifluoromethyl)phenyl)boronic acid (69.48 mmol, 13194 mg), potassium carbonate (52.11 mmol, 7202 mg), and Pd(dppf)Cl2(1.303 mmol, 953 mg) were stirred in dry THF (120 mL) and water (30 mL) at 80 °C under argon for 120 minutes. The reaction mixture was cooled to room temperature, the THF evaporated in vacuo, acidified with 12H N HCl to pH ~1, the residue dissolved in DCM, filtered through a polypropylene frit to retain water, eluting DCM, added ~40g of flash silica gel to the DCM, evaporated to dryness in vacuo, packed into a loader, and purified by flash chromatography on silica gel (220g, 0% acetone / DCM (2 CV) → 10% (10 CV)). Fractions containing product were evaporated to dryness in vacuo to give a light yellow hard foam, 3206 mg (27% yield from tribromo). MS (APCI): calculated for Chemical Formula: C36H22F9NO3(M+H) 688; found: 688.1H NMR (400 MHz, TCE) δ 8.80 (d, J = 1.8 Hz, 1H), 8.50 (s, 1H), 8.05 (d, J = 1.8 Hz, 1H), 7.94 – 7.84 (m, 4H), 7.80 (d, J = 8.0 Hz, 2H), 7.68 (d, J = 8.1 Hz, 2H), 7.60 (d, J = 8.0 Hz, 2H), 7.47 (d, J = 8.0 Hz, 2H), 3.54 (q, J = 6.0 Hz, 2H), 1.85 (p, J = 6.5 Hz, 2H). Compound GN-8.4 (2-(3-chloropropyl)-5,6,8-tris(4-(trifluoromethyl)phenyl)-1H- benzo[de]isoquinoline-1,3(2H)-dione): Compound GN-8.3 (4.663 mmol, 3206 mg) and 2-chloro-1,-3-dimethylimidazolium hexafluorophosphate (6.062 mmol, 1689 mg) were stirred in dry DMF (25 mL) at 100 °C under argon for 60 minutes. The reaction mixture was cooled to room temperature, the product precipitated by adding water, the product filtered off, washing with water, the residue dissolved in DCM, filtered through a polypropylene frit to retain water, eluting DCM, most of the DCM evaporated, the residue diluted ~1:1 with hexanes, loaded onto ~40g of flash silica gel packed into a loader, and purified by flash chromatography on silica gel (120g, 0% acetone / hexanes (2 CV) → 50% (10 CV), stop at 9.0%, isocratic). Fractions containing product were evaporated to dryness in vacuo to give a light yellow, hard foam, 2396 mg (73% yield). MS (APCI): calculated for Chemical Formula: C36HClF9NO2(M+H) 706; found: 706.1H NMR (400 MHz, DMSO) δ 8.80 (d, J = 1.8 Hz, 1H), 8.50 (s, 1H), 8.05 (d, J = 1.7 Hz, 1H), 7.90 (d, J = 8.6 Hz, 2H), 7.87 (d, J = 8.9 Hz, 2H), 7.80 (d, J = 8.1 Hz, 2H), 7.68 (d, J = 8.1 Hz, 2H), 7.59 (d, J = 8.0 Hz, 2H), 7.47 (d, J = 8.0 Hz, 2H), 4.26 (t, J = 6.9 Hz, 2H), 3.78 (t, J = 6.5 Hz, 2H), 2.17 (p, J = 6.7 Hz, 2H). Compound GN-8.5 (3-(1,3-dioxo-5,6,8-tris(4-(trifluoromethyl)phenyl)-1H- benzo[de]isoquinolin-2(3H)-yl)propyl 2-isopropyl-4-methyl-1H-pyrrole-3- carboxylate): Compound GN-8.14(3.394 mmol, 2396 mg), 2-isopropyl-4-methyl-1H- pyrrole-3-carboxylic acid (WuXi AppTech, 4.412 mmol, 783 mg), and potassium carbonate (6.788 mmol, 938 mg) were stirred in dry DMF (25 mL) at 100 °C under argon for 90 minutes, then cooled to room temperature. The mixture was diluted with water (~100 mL), acidified to pH ~1 with 6N HCl, diluted with another 300 mL of water, stirred for 20 minutes, then the precipitate was filtered off, washing with water. The residue was dissolved in DCM, filtered through a polypropylene frit to retain water, eluting with DCM, the DCM evaporated, the residue taken up in DCM, diluted with some hexanes, loaded onto ~40g of flash silica gel in a loader, and purified by flash chromatography on silica gel (120g, 0% acetone / hexanes (2 CV) → 50% (10 CV), stop at 22.0%, isocratic). Fractions containing product were evaporated to dryness in vacuo to give a hard, light-yellow foam, 2676 mg (94% yield). MS (APCI): calculated for Chemical Formula: C45H33F9N2O4(M+H) 837; found: 837.1H NMR (400 MHz, DMSO) δ 10.71 (s, 1H), 8.76 (d, J = 1.7 Hz, 1H), 8.45 (s, 1H), 8.02 (d, J = 1.7 Hz, 1H), 7.87 (d, J = 1.5 Hz, 4H), 7.79 (d, J = 8.1 Hz, 2H), 7.67 (d, J = 8.1 Hz, 2H), 7.58 (d, J = 8.0 Hz, 2H), 7.45 (d, J = 8.0 Hz, 2H), 6.34 (dd, J = 2.5, 1.2 Hz, 1H), 4.29 (t, J = 6.9 Hz, 2H), 4.23 (t, J = 6.0 Hz, 2H), 3.65 (p, J = 7.0 Hz, 1H), 2.09 (d, J = 1.0 Hz, 3H), 1.11 (d, J = 7.0 Hz, 6H). Compound GN-8.7 (bis(3-(1,3-dioxo-5,6,8-tris(4-(trifluoromethyl)phenyl)-1H- benzo[de]isoquinolin-2(3H)-yl)propyl) 10-(4-acetoxy-2,6-dimethylphenyl)-5,5- difluoro-3,7-diisopropyl-1,9-dimethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'- f][1,3,2]diazaborinine-2,8-dicarboxylate): Compound GN-8.5 (3.198 mmol, 2676 mg), Compound GN-8.6 (1.599 mmol, 307 mg), and pTsOH.H2O (0.3198 mmol, 61 mg) were stirred in dry DCE (50 mL) at 60 °C under argon for 90 minutes, then cooled to room temperature. The reaction mixture was treated with DDQ (2.878 mmol, 653 mg), stirred at room temperature for 10 minutes, at which point oxidation was done, treated with triethylamine (12.79 mmol, 1.8 mL), BF3.OEt2(19.19 mmol, 2.4 mL). The triethylamine (12.79 mmol, 1.8 mL), BF3.OEt2(19.19 mmol, 2.4 mL) treatment was repeated, and the mixture heated to 60 °C for 3 hours, then room temperature overnight. The reaction mixture was quenched with 30 mL saturated sodium bicarbonate solution, stirred for 10 minutes, then filtered through a polypropylene frit to retain water, eluting with DCM. The DCM was evaporated to dryness in vacuo, the residue taken up in a small volume of DCM, loaded onto ~40g of flash silica gel packed into a loader, and purified by flash chromatography on silica gel (120g, 0% acetone / hexanes (2 CV) → 30% (10 CV), stop at 16.0%, isocratic). Fractions containing product were evaporated to dryness in vacuo to give an orange solid, 2241 mg (74% yield). MS (APCI): calculated for Chemical Formula: C101H73BF20N4O10(M+H) 1894; found: 1894.1H NMR (400 MHz, TCE) δ 8.88 (d, J = 1.7 Hz, 2H), 8.65 (s, 2H), 8.08 (d, J = 1.8 Hz, 2H), 7.76 (d, J = 8.4 Hz, 4H), 7.71 (d, J = 3.7 Hz, 4H), 7.69 (d, J = 3.6 Hz, 4H), 7.53 (d, J = 8.2 Hz, 4H), 7.40 (d, J = 7.9 Hz, 4H), 7.28 (d, J = 8.0 Hz, 4H), 6.94 (s, 2H), 4.49 – 4.27 (m, 8H), 3.84 (p, J = 7.0 Hz, 2H), 2.35 – 2.19 (m, 7H), 2.09 (s, 6H), 1.57 (s, 6H), 1.39 (d, J = 7.0 Hz, 12H). Compound GN-8 (bis(3-(1,3-dioxo-5,6,8-tris(4-(trifluoromethyl)phenyl)-1H- benzo[de]isoquinolin-2(3H)-yl)propyl) 10-(4-acetoxy-2,6-dimethylphenyl)-5,5- dicyano-3,7-diisopropyl-1,9-dimethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'- f][1,3,2]diazaborinine-2,8-dicarboxylate): Compound GN-8.7 (1.000 mmol, 1893 mg), TMSCN (10.00 mmol, 1.3 mL), and BCl3(1.0M tol, 1.000 mmol, 1.0 mL) were stirred in dry DCE (30 mL) at 50 °C overnight. The reaction mixture was cooled to room temperature, quenched with 30 mL of 10% citric acid solution, stirred for 10 minutes, filtered through a polypropylene frit to retain water, eluting DCM, the DCM was evaporated to dryness in vacuo, dissolved in DCM / hexanes, loaded onto ~40g of flash silica gel packed into a loader, and purified by flash chromatography on silica gel (120g, 0% acetone / hexanes (2 CV) → 25% (10 CV), stop at 16.0%, then 16.5%, isocratic at each step). Fractions containing product were evaporated to dryness, and the residue was resubmitted to the reaction conditions, then worked up and purified by flash chromatography on silica gel (load onto ~40g of flash silica gel packed into a loader by dissolving in toluene, 120g, 0% acetone / toluene (2 CV) → 5% (10 CV), stop at 2.2%, back to 2.1 %, isocratic at each step). Fractions containing product were evaporated to dryness in vacuo to give an orange solid, 1330 mg (70% yield). MS (APCI): calculated for Chemical Formula: C103H73BF18N6O10(M+H) 1908; found: 1908.1H NMR (400 MHz, TCE) δ 8.89 (d, J = 1.7 Hz, 2H), 8.67 (s, 2H), 8.09 (d, J = 1.8 Hz, 2H), 7.76 (d, J = 8.4 Hz, 4H), 7.74 – 7.66 (m, 8H), 7.55 (d, J = 8.1 Hz, 4H), 7.40 (d, J = 7.9 Hz, 4H), 7.29 (d, J = 8.0 Hz, 5H), 7.00 (s, 2H), 4.44 (t, J = 6.7 Hz, 4H), 4.37 (t, J = 7.1 Hz, 4H), 3.88 (p, J = 6.9 Hz, 2H), 2.33 – 2.21 (m, 7H), 2.17 (s, 6H), 1.65 (s, 6H), 1.59 (d, J = 6.8 Hz, 12H). Synthesis procedure for GN-9 Compound GN-9.1 (4-formyl-3,5-dimethylphenyl acetate): 4-hydroxy-2,6- dimethylbenzaldehyde (50.00 mmol, 7505 mg) and DMAP (100.0 mmol, 12.220 g) were combined in dry DCM (100 mL) and stirred under argon at room temperature. To the reaction was added acetic anhydride (75.00 mmol, 7.1 mL). The reaction was stirred for 15 minutes at room temperature, then quenched with a few drops of acetic acid. The reaction mixture was reduced in volume in vacuo and loaded onto ~60g of flash silica gel packed into a loader and purified by flash chromatography on silica gel (120g, 0% EtOAc / hex (2 CV) → 15% (10 CV)). Fractions containing product were evaporated to dryness in vacuo to give a colorless oil, 4.890 g (51% yield). MS (APCI): calculated for Chemical Formula: C11H12O3(M+H) = 193; found: 193.1H NMR (400 MHz, TCE) δ 10.55 (s, 1H), 6.87 (s, 2H), 2.62 (s, 6H), 2.32 (s, 3H). Compound GN-9 (diethyl 10-(4-acetoxy-2,6-dimethylphenyl)-5,5-difluoro-1,3,7,9- tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8- dicarboxylate): Compound GN-9.1 (17.75 mmol, 3412 mg), ethyl 2,4-dimethyl-1H- pyrrole-3-carboxylate (35.50 mmol, 5936 mg), and pTsOH.H2O (1.775 mmol, 338 mg) were stirred in dry DCE (100 mL) under argon at 40 °C for 90 minutes and then cooled to room temperature. DDQ (26.63 mmol, 6044 mg) was added and the mixture stirred for 10 minutes. Et3N (71.01 mmol, 9.90 mL), and BF3.OEt2(106.5 mmol, 13.1 mL) were added to the reaction. The addition of Et3N (71.01 mmol, 9.90 mL), and BF3.OEt2(106.5 mmol, 13.1 mL) was repeated and the reaction stirred at 50 °C for 30 minutes. The reaction mixture was cooled to room temperature and quenched with 50 mL water and stirred for 5 minutes. The reaction mixture was filtered through a polypropylene frit to retain water. The frit was eluted with DCM. The organic eluent was evaporated onto 50g of flash silica gel in vacuo and packed into a loader. It was purified by flash chromatography on silica gel (330g, 0% EtOAc / DCM (2 CV) → 10% (5 CV), stopping gradient at 4.0%, then 6.2%). Fractions containing product were evaporated to dryness in vacuo, triturated with hot MeOH, adding water while hot to ~50%, cooled to room temperature, and filtered off the precipitate, washing with 50% MeOH / water. The product was dried in vacuo to give an orange solid, 6528 mg (66% yield). MS (APCI): calculated for Chemical Formula: C29H33BF2N2O6(M-H) = 555 found: 555.1H NMR (400 MHz, TCE) δ 6.99 (s, 2H), 4.28 (q, J = 7.1 Hz, 4H), 2.84 (s, 6H), 2.14 (s, 6H), 1.72 (s, 6H), 1.34 (t, J = 7.1 Hz, 6H). Synthesis procedure for GN-10 Compound GN-10.1 (diethyl 5,5-difluoro-10-(4-hydroxy-2,6-dimethylphenyl)-1,3,7,9- tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8- dicarboxylate): A 1 L 3N round bottom flask was placed in an aluminum heat block and charged with a stir bar. The flask was fitted with a finned condenser / gas adapter, stopper and flow control valve. The system was flushed with argon. To the flask was added ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (30.0 mmol, 5.016 g) and 4-hydroxy-2,6- dimethylbenzaldehyde (15.0 mmol, 2.253 g), followed by anhydrous dichloroethane (250 mL). Under argon atmosphere, the reaction mixture was stirred and sparged with nitrogen gas for 15 minutes. To the flask was added pTsOH.H2O (1.50 mmol, 285 mg) and nitrogen sparging was continued for another 15 minutes. The nitrogen sparge was stopped and the reaction mixture was stirred at room temperature under argon atmosphere overnight. To the flask was added DDQ (18.0 mmol, 4.086 g) and the reaction stirred under argon for 90 minutes. The reaction mixture was cooled to 0 °C (ice-water bath) and treated successively with Et3N (60.0 mmol, 8.36 mL) and BF3.OEt2(90.0 mmol, 11.1 mL). The reaction mixture was stirred at 0 °C for 2 minutes, then placed back in the heat block and heated to 50 °C for 1 hour. The addition of Et3N (60.0 mmol, 8.36 mL) and BF3.OEt2(90.0 mmol, 11.1 mL) was repeated and the reaction mixture stirred at 50 °C for an additional hour. The addition of Et3N (30.0 mmol, 4.2 mL) and BF3.OEt2(45.0 mmol, 6.5 mL) was further repeated and stirred at 50 °C for an additional hour. The crude reaction mixture was split into thirds. Each third was loaded onto a solid loader containing 65g of flash silica gel and there was repeated purification by flash chromatography on silica gel 3 times (330g, solid load, equilibrate 100% hexanes, eluting 100% hexanes (2 CV) → 30% EtOAc / hexanes (30 CV)). Fractions containing product from all three columns were combined and evaporated to dryness in vacuo to give an orange solid, 6.1068 g (80% yield). MS (APCI): calculated for Chemical Formula: C48H52BBr2F2N3(M-) = 512; found: 512.1H NMR (400 MHz, Tetrachloroethane-d2) δ 6.70 (s, 2H), 4.28 (q, J = 7.1 Hz, 4H), 2.83 (s, 6H), 2.07 (s, 6H), 1.74 (s, 6H), 1.34 (t, J = 7.1 Hz, 6H). Compound GN-10 (diethyl 10-(4-(2-(4-(1,3-dioxo-5,11-bis(4- (trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)- yl)phenyl)acetoxy)-2,6-dimethylphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4l4,5l4- dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylate): Compound GN-10.1 (0.3000 mmol, 154 mg), 2-(4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H- xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid (0.3600 mmol, 255 mg), DMAP.pTsOH salt (0.03000 mmol, 9 mg) and DIC (0.6000 mmol, 0.094 mL) were stirred in dry DCM (10 mL) at room temperature for one hour. The crude reaction was loaded onto ~30g of flash silica gel packed into a loader and purified by flash chromatography on silica gel (120g, 0% EtOAc / DCM (2 CV) → isocratic steps to 3.8% EtOAc / DCM, then isocratic to elute product). Fractions containing product were evaporated to dryness in vacuo To give an orange solid, 304 mg (84% yield). MS (APCI): calculated for Chemical Formula: C67H50BF8N3O9(M+H) = 1204; found: 1204.1H NMR (400 MHz, TCE) δ 8.71 (s, 1H), 8.48 (s, 1H), 7.91 (d, J = 8.2 Hz, 2H), 7.89 – 7.82 (m, 4H), 7.72 – 7.63 (m, 4H), 7.48 – 7.37 (m, 3H), 7.31 (dd, J = 8.3, 1.3 Hz, 1H), 7.10 (dd, J = 8.3, 1.5 Hz, 1H), 7.05 (s, 2H), 6.96 (ddd, J = 8.4, 7.1, 1.3 Hz, 1H), 4.29 (q, J = 7.1 Hz, 4H), 4.02 (s, 2H), 2.84 (s, 6H), 2.16 (s, 6H), 1.74 (s, 6H), 1.34 (t, J = 7.1 Hz, 6H). Synthesis procedure for GN-11 Compound GN-11.2 (2-(5,11-dibromo-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin- 2(3H)-yl)ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate): Compound GN-11.1 (16.00 mmol, 5927 mg), 5,11-dibromo-1H,3H-isochromeno[6,5,4-mna]xanthene-1,3-dione (WuXi AppTech, 10.70 mmol, 4773 mg), DMAP (2.140 mmol, 262 mg) and triethylamine (107 mmol, 14.9 mL) were stirred in dry DMF (50 mL) at 90 °C under argon for 4 hours, then RT overnight. The reaction mixture was poured into ~500 mL of stirred water, the precipitate filtered off, and dried by suction. It was used damp and as-is in the next step. It was too insoluble for NMR. MS (APCI): calculated for Chemical Formula: C27H18Br2N2O5(M+H) 1609; found: 1609. Compound GN-11.3 (2-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H- xantheno[2,1,9-def]isoquinolin-2(3H)-yl)ethyl 2,4-dimethyl-1H-pyrrole-3- carboxylate): Compound GN-11.2 (assume 100%, 10.70 mmol, 6830 mg), (3,5- bis(trifluoromethyl)phenyl)boronic acid (42.80 mmol, 11038 mg), potassium carbonate (58.85 mmol, 8134 mg), and Pd(dppf)Cl2(1.070 mmol, 783 mg) were stirred in dry THF (120 mL) and water (20 mL) under argon at 80 °C for 30 minutes, then cooled to room temperature. Most of the THF was evaporated in vacuo, the residue acidified with 12N HCl to pH ~1, partitioned between water and DCM, filtered through a polypropylene frit to retain water, eluting with DCM. The DCM was evaporated in vacuo, the residue taken up in a small volume of DCM, ~40g of flash silica gel added, the DCM removed in vacuo, the silica gel packed into a loader, and purified by flash chromatography on silica gel (220g, 0% acetone / hexanes (2 CV) → 50% (10 CV), stop at 14.0%, 20.0%, 25.0%, and 35.0%, isocratic at each step). Fractions containing product were evaporated to dryness in vacuo to give a yellow solid, 1792 mg (19% yield from dibromo-anhydride). MS (APCI): calculated for Chemical Formula: C45H28F12N2O5(M+H) 905; found: 905.1H NMR (400 MHz, TCE) δ 8.75 (s, 1H), 8.49 (s, 1H), 8.30 – 8.22 (m, 2H), 8.06 (s, 2H), 8.01 (t, J = 2.8 Hz, 3H), 7.47 (dt, J = 8.5, 4.4 Hz, 1H), 7.28 – 7.23 (m, 1H), 6.98 (d, J = 4.3 Hz, 2H), 6.37 (dd, J = 2.4, 1.2 Hz, 1H), 4.59 (dt, J = 10.9, 5.5 Hz, 4H), 3.68 (p, J = 6.9 Hz, 1H), 2.14 (d, J = 1.0 Hz, 3H), 1.17 (d, J = 7.0 Hz, 6H). Compound GN-11 (bis(2-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H- xantheno[2,1,9-def]isoquinolin-2(3H)-yl)ethyl) 10-(4-acetoxy-2,6-dimethylphenyl)- 5,5-difluoro-3,7-diisopropyl-1,9-dimethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'- f][1,3,2]diazaborinine-2,8-dicarboxylate): Compound GN-11.3 (1.981 mmol, 1792 mg), Compound GN-11.4 (0.9904 mmol, 190 mg), and pTsOH.H2O (0.1981 mmol, 38 mg) were stirred in dry DCE (50 mL) at 65 °C for 90 minutes, then cooled to room temperature. The reaction was treated with DDQ (1.486 mmol, 337 mg) and stirred at room temperature for 10 minutes, at which point the oxidation was done. The reaction mixture was treated with triethylamine (7.923 mmol, 1.1 mL), BF3.OEt2(11.88 mmol, 1.5 mL). The triethylamine (7.923 mmol, 1.1 mL), BF3.OEt2(11.88 mmol, 1.5 mL) treatment was repeated, and the mixture heated to 65 °C for 90 minutes, then cooled to room temperature. The reaction mixture was quenched with 50 mL saturated sodium bicarbonate solution, stirred for 10 minutes, then filtered through a polypropylene frit to retain water, eluting with DCM. The DCM was evaporated to dryness in vacuo, the residue taken up in a small volume of toluene, loaded onto ~40g of flash silica gel packed into a loader, and purified by flash chromatography on silica gel (120g, 0% EtOAc / toluene (2 CV) → 5.0% (10 CV), stop at 3.1%, isocratic). Fractions containing product were evaporated to dryness in vacuo to give an orange solid, 1073 mg (63% yield). Too big for MS.1H NMR (400 MHz, TCE) δ 8.71 (s, 2H), 8.46 (s, 2H), 8.26 (d, J = 1.6 Hz, 4H), 8.06 (s, 2H), 8.02 (s, 2H), 8.01 (d, J = 1.6 Hz, 4H), 7.48 (ddd, J = 8.5, 5.6, 3.1 Hz, 2H), 7.26 (d, J = 8.1 Hz, 3H), 7.23 - 7.14 (m, 1 H), 7.04 - 6.94 (m, 4H), 6.83 (s, 2H), 4.59 (s, 8H), 3.77 (p, J = 7.0 Hz, 2H), 2.21 (s, 3H), 2.04 (s, 6H), 1.52 (s, 6H), 1.33 (d, J = 6.9 Hz, 12H). Synthesis procedure for RD-1

[0055] General procedure of compound RD-1.1 synthesis — (E)-1-(4-isobutylphenyl)-3-(4- (trifluoromethyl)phenyl)prop-2-en-1-one: A 100 mL flask was fitted with a stir bar. To the flask, compound (4-isobutylphenyl) methyl ketone (2.0 g, 11.3 mmol) and 4- trifluoromethylbenzaldehyde (2.1 g, 11.9 mmol) with EtOH (15 ml) were added. To the solution, NaOH (2.7 mL, 5 M in H2O) was added dropwise. After the addition, the reaction mixture was kept at room temperature for 1 hour. TLC and LCMS showed the completion of the reaction. The reaction mixture was diluted with 50 mL of H2O. The product was collected by vacuum filtration and washed by 50 mL of H2O, then further dried by lyophilization to provide RD1.1 as a white solid for the next step without further purification.3.66 g, 97% yield. MS (APCI): calculated for Chemical Formula: C20H19F3O ([M-H]-) = 332 found: 332.1H NMR (400 MHz, CDCl3) 7.96 (m, 2H), 7.79 (d, J = 16.0 Hz, 1H), 7.77 (m, 2H), 7.70 (m, 2H), 7.61 (d, J = 16.0 Hz, 1H), 7.32 (m, 2H), 2.58 (d, J = 7.2 Hz, 2H), 1.93 (m, 1H), 0.94 (d, J = 6.8 Hz, 6H). General procedure of compound RD-1.2 synthesis— 1-(4-isobutylphenyl)-4-nitro-3- (4-(trifluoromethyl)phenyl)butan-1-one: A 100 mL flask was fitted with a stir bar. To the flask, compound RD-1.1 (2.0 g, 6.0 mmol), Nitromethane (7 mL) and EtOH (7 mL) were added. To the mixture, KOH (67.3 mg, 1.2 mmol) was added. The reaction mixture was degassed at room temperature, and then heated up to 95 °C and kept at this temperature for 30 minutes. LCMS was used to monitor the reaction. After the completion, the reaction was cooled down to room temperature, and worked up by the addition of H2O (150 ml). The solution was extracted with EtOAc (100 mL *3). A small amount of NaCl was added during the extraction to assist the separation of organic phase from aqueous phase. The combined organic phase was dried over anhydrous Na2SO4 and concentrated by rotavapor to provide RD-1.2 as a brown liquid, which has been used for the next step without further purification. Quantitative yield. MS (APCI): calculated for Chemical Formula: C21H22F3NO3([M+H]+) = 394 found: 394.1H NMR (400 MHz, CDCl2CDCl2) 7.83 (m, 2H), 7.62 (m, 2H), 7.44 (m, 2H), 7.25 (m, 2H), 4.88 (dd, J = 12.8 Hz, 6.0 Hz, 1H), 4.71 (dd, J = 12.8 Hz, 8.4 Hz, 1H), 4.29 (m, 1H), 3.43 (qd, J = 18.0 Hz, 7.6 Hz, 2H), 2.53 (d, J = 7.2 Hz, 2H), 1.87 (m, 1 H), 0.90 (d, J = 7.8 Hz, 6H), General procedure of compound RD-1.3 synthesis—1-(4-isobutylphenyl)-4,4- dimethoxy-3-(4-(trifluoromethyl)phenyl)butan-1-one: A 250 mL flask was fitted with a stir bar. To the flask, compound RD-1.2 (2.4 g, 6.0 mmol), THF (67 mL) and MeOH (34 ml) were added. To the solution, KOH (841.7 mg, 15.0 mmol) was added in one portion. The solution was kept at room temperature for 1 hour. Meanwhile, a solution of H2SO4(8 mL) in MeOH (36 mL) was cooled down to 0 ºC. Then the previous solution was added to the H2SO4solution dropwise via addition funnel at 0 °C. After addition, the reaction was warmed up to room temperature. The reaction was kept at room temperature for another 1 hour. LCMS showed the completion of the reaction. The reaction solution was poured into crashed ice and was extracted with EtOAc (150 ml *3). The combined organic phase was washed with 10% (w / w) Na2CO3in H2O and then brine. After being dried over anhydrous Na2SO4, the solution was concentrated under vacuum rotavapor to provide RD-1.3 as a brown oil, which was used for the next step without further purification. MS (APCI): calculated for Chemical Formula: C23H27F3O3([M-OMe]+) = 378 found: 378.1H NMR (400 MHz, CDCl2CDCl2) 7.83 (m, 2H), 7.55 (m, 2H), 7.46 (m, 2H), 7.22 (m, 2H), 4.46 (d, J = 5.2 Hz, 1H), 3.78 (td, J = 9.2 Hz, 5.2 Hz, 1H), 3.54 (dd, J = 17.6 Hz, 4.8 Hz, 1H), 3.39 (dd, J = 17.6 Hz, 8.8 Hz, 1H), 3.38 (s, 3H), 3.32 (s, 3H), 2.52 (d, J = 7.2 Hz, 1H), 1.88 (m, 1H), 0.90 (d, J = 6.4 Hz, 6H). General procedure of compound RD-1.4 synthesis— 2-(4-isobutylphenyl)-4-(4- (trifluoromethyl)phenyl)-1H-pyrrole: A 100 ml flask was charged with RD-1.3 (2.5 g, 6.0 mmol) and NH4•OAc (2.2 g, 29.2 mmol) in AcOH (7.2 mL). The solution was degassed at room temperature. Then it was heated up to 100 ºC and was kept stirring at this temperature for 5 hours. TLC (50% EtOAc in Hexane) showed the completion of the reaction. The reaction mixture was quenched by the addition of H2O (40 mL) and extracted with DCM (60 mL*3). The combined organic phase was washed with saturated NaHCO3and brine. After being dried over anhydrous Na2SO4, the solution was concentrated under rotavapor and was purified by silica gel flash chromatography using DCM in Hexane (0%-100%) as an eluant to provide pure compound RD-1.4 as a light gray blue solid, 1.6 g, 78% yield over three steps. MS (APCI): calculated for Chemical Formula: C21H20F3N ([M-H]-) = 343 found: 343.1H NMR (400 MHz, CDCl2CDCl2) δ 8.60 (s, 1H), 7.67 (m, 2H), 7.62 (m, 2H), 7.45 (m, 2H), 7.20 (m, 3H), 6.82 (m, 1H), 2.50 (d, J = 7.2 Hz, 1H), 1.89 (m, 1H), 0.93 (d, J = 6.4 Hz, 1H). General procedure of compound RD-1.5 synthesis— 4-(5,5-difluoro-3,7-bis(4- isopentylphenyl)-1,9-bis(4-(trifluoromethyl)phenyl)-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'- f][1,3,2]diazaborinin-10-yl)-3,5-dimethylphenol: A 100 mL 2 neck round bottomed flask was fitted with an air condenser and a stir bar. To the flask, RD-1.4 (686.8 mg, 2.0 mmol) and 4-hydroxyl-2,6-dimethylbenzaldehyde (150.2 mg, 1.0 mmol) were added, followed by anhydrous dichloroethane (22 ml). The reaction mixture was sparged with Ar for 30 minutes, then p-TsOH•H2O (34.2 mg, 0.2 mmol) was added. The reaction solution was heated up to 60 °C and kept at this temperature overnight. Then the reaction was cooled down to room temperature and DDQ (454.0 mg, 2.0 mmol) was added. The reaction was kept at room temperature for 30 minutes. Then BF3•OEt2 (1.5 mL, 12.0 mmol) and Et3N (1.1 mL, 8.0 mmol) were added at room temperature. The reaction mixture was heated up to 50 °C and kept at this temperature for 2 hours. The reaction mixture was loaded with silica gel and purified by flash chromatography, using DCM in Hexane (0-100%) as an eluant to provide the pure RD-1.5 as a dark purple blue solid, 669.0 mg, 77% yield. MS (APCI): calculated for Chemical Formula: C51H45BF8N2O ([M-H]-) = 864 found: 864.1H NMR (400 MHz, CDCl2CDCl2) 7.88 (m, 4H), 7.27 (m, 4H), 7.19 (4H), 6.90 (m, 4H), 6.55 (s, 2H), 5.70 (s, 2H), 4.40 (bs, 1H), 2.54 (d, J = 7.2 Hz, 4H), 1.96 (s, 6H), 1.93 (m, 2H), 0.94 (d, J = 6.4 Hz, 12H). General procedure of compound RD-1 synthesis— 4-(5,5-difluoro-3,7-bis(4- isobutylphenyl)-1,9-bis(4-(trifluoromethyl)phenyl)-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'- f][1,3,2]diazaborinin-10-yl)-3,5-dimethylphenyl 2-(4-(1,3-dioxo-9-(4- (trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate: A 25 mL vial was fitted with a stir bar. To the vial, compound RD-1.5 (43.2 mg, 0.05 mmol), 1621-29 (40.0 mg, 0.07 mmol), DIC (25.2 mg, 0.20 mmol) and DMAP•TsOH (29.4 mg, 0.10 mmol) were added, followed by anhydrous DCM (5 ml). The reaction mixture was kept at room temperature overnight. The reaction mixture was loaded with silica gel and purified by flash chromatography, using EtOAc in DCM (0-8%-10%) as the eluants to provide a dark purple red solid. The solid was further triturated with MeOH (10 ml) to deliver RD-1, 19.0 mg, 27% yield. MS (APCI): calculated for Chemical Formula: C84H61BF11N3O5([M-H]-) = 1411 found: 1411.1H NMR (400 MHz, CDCl2CDCl2) 8.70 (d, J = 8.0 Hz, 1H), 8.66 (d, J = 8.0 Hz, 1H), 8.30 (d, J = 2.0 Hz, 1H), 8.12 (d, J = 8.0 Hz, 1H), 7.85 (m, 9H), 7.55 (m, 3H), 7.40 (m, 3H), 7.26 (m, 8H), 6.90 (m, 4H), 6.56 (s, 2H), 6.16 (s, 2H), 3.85 (s, 2H), 2.56 (d, J = 6.8 Hz, 4H), 2.04 (s, 6H), 1.93 (m, 2H), 0.94 (d, J = 7.4 Hz, 12H).

[0056] Synthesis procedure for RD-2 Synthesis procedure for Compound FD-4 Compound FD-1.1 (6-(2-nitrophenoxy)-1H,3H-benzo[de]isochromene-1,3-dione): A mixture of 2-nitrophenol (6.6g, 48 mmol), KOH powder (2.4g, 43 mmol) was mixed and stirred under vacuum for 30 min, then copper powder (0.4 g) was added, followed by 100 mL anhydrous DMF. The mixture was stirred for 5 min, then 4-chloronaphthalic anhydride (5.1g, 22 mmol) was added. The whole was degassed then heated at reflux for 1.5 hr. After being cooled to room temperature, 100mL 20% hydrochloric acid was added dropwise into the resultant reaction mixture, which was allowed to sit for 2 hrs. The precipitate was collected by filtration, then was dried under vacuum overnight to give a yellow brown solid (4.6g). It was further purified by stirring in refluxing acetic acid (50 mL) for 1 hr, then cooled to room temperature. After filtration and drying in air a yellow solid (3.0g, in 41% yield) was provided. Confirmed by LCMS (APCI): calcd for C18H10NO6(M+H): 336.0; Found: 336.1H NMR (400 MHz, Chloroform-d) δ 8.80 (dd, J = 8.5, 1.2 Hz, 1H), 8.72 (dd, J = 7.3, 1.2 Hz, 1H), 8.50 (d, J = 8.2 Hz, 1H), 8.19 (dd, J = 8.2, 1.7 Hz, 1H), 7.90 (dd, J = 8.5, 7.3 Hz, 1H), 7.79 (td, J = 7.9, 1.7 Hz, 1H), 7.54 (td, J = 8.0, 1.3 Hz, 1H), 7.39 (dd, J = 8.3, 1.2 Hz, 1H), 6.89 (d, J = 8.2 Hz, 1H). Compound FD-1.2 (6-(2-aminophenoxy)-1H,3H-benzo[de]isochromene-1,3-dione): A mixture of Compound FD-1.1 (2.0g, 6 mmol) and iron powder (<10um, 0.91g, 16 mmol) in acetic acid (75 mL) was heated to reflux for 30 min. The resulting solution was poured into water (220mL). The resulting precipitate was collected by filtration and washed with water and dried thoroughly in air then under vacuum to afford a yellow solid (1.65g, in 90% yield). Confirmed by LCMS (APCI): calcd for C18H12NO4(M+H): 306.1; Found: 306. Compound FD-1.3 (1H,3H-isochromeno[6,5,4-mna]xanthene-1,3-dione): Compound FD-1.2 (1.5g, 4.9mmol) was dispersed in acetic acid (35mL) and cooled to 0 °C. While being stirred, precooled hydrochloric acid (3mL, 37 mmol) was added, then sodium nitrite solution (3.29g, 46 mmol) in 12 mL water was added dropwise at 0 °C. The whole was stirred for one hour at 0 °C, then was transferred into an addition funnel, and dropped into a refluxed copper sulfate solution (5.08g, 20 mmol, in 50 mL water) over a one hour period. After cooling to room temperature, the precipitate was collected by filtration, washed with water and acetone, then dried in air, then in vacuum to give a yellow solid (0.92g, in 65% yield). Confirmed by LCMS (APCI): Calcd for C18H8O4(M-): 288.0; Found: 288. Compound FD-4.1 (5,11-dibromo-1H,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. To the flask was added Compound FD-3.1 (34.688 mmol, 10.00 g), followed by ortho-dichlorobenzene (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 with an aluminum heat block 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 to give orangish solids, 10.866 g total (69.9% yield). Both had similar LCMS and NMR. MS (APCI): calculated for Chemical Formula: C18H6Br2O4(M+H) = 445; found: 445.1H NMR (400 MHz, TCE) δ 9.47 (dd, J = 8.4, 1.5 Hz, 1H), 8.76 (d, J = 14.2 Hz, 2H), 7.72 – 7.63 (m, 1H), 7.56 (dd, J = 8.3, 1.4 Hz, 1H), 7.46 (ddd, J = 8.5, 6.7, 1.9 Hz, 1H). Compound FD-4.2 (2-(4-(5,11-dibromo-1,3-dioxo-1H-xantheno[2,1,9- def]isoquinolin-2(3H)-yl)phenyl)acetic acid): A 100 mL 2N round bottom flask was charged with a stir bar and fitted with a finned condenser / gas adapter and flow control. The system was flushed with argon. To the flask was added Compound FD-4.1 (7.000 mmol, 3.136 g), 2-(4-aminophenyl)acetic acid (14.00 mmol, 2.117 g), DMAP (2.100 mmol, 257 mg), and anhydrous DMF (65 mL). The reaction mixture was heated in an aluminum block set to 160 °C for 5 hours. The crude reaction mixture was cooled to 0 °C and quenched with 6N HCl (~5 mL) and diluted with water (up to ~350 mL). The precipitate was filtered off, washing with water. The product was dried by suction and used without further purification in the next reactions. Assume 100% yield. MS (APCI): calculated for Chemical Formula: C26H13Br2NO5(M+H) = 578; found: 578. Compound FD-4.3(1655-22) (2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3- dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid): A 250 mL 2N round bottom flask was charged with a stir bar and fitted with a finned condenser / gas adapter and flow control. The system was flushed with argon. To the flask was added Compound FD-4.2 (3.500 mmol, 2.034 g), (3,5- bis(trifluoromethyl)phenyl)boronic acid (14.00 mmol, 3.611), K2CO3(19.25 mmol, 2.661 g), THF (60 mL), DMF (12 mL), and water (6 mL). The reaction mixture was stirred under argon at room temperature for a few minutes, then Pd(dppf)Cl2(0.0245 mmol, 179 mg) was added. The headspace was flushed with argon for a minute, then the flow control was closed. The reaction mixture was stirred and heated in an aluminum heat block at 80 °C for three hours. The crude reaction mixture was evaporated to dryness in vacuo, taken up in DCM, and evaporated in vacuo onto ~35 g of flash silica gel. It was purified by flash chromatography on silica gel (220g, equilibrate 0% EtOAc / DCM, eluting 0% (10 CV) → 15.3% EtOAc / DCM (15.3 CV) → 40% EtOAc / DCM (10 CV) → isocratic 40% EtOAc / DCM) EtOAc contains 0.1% v / v TFA to give a brownish-yellow solid, 1.710 g (57.6% yield). MS (APCI): calculated for Chemical Formula: C42H19F12NO5(M+H) = 846; found: 846.1H NMR (400 MHz, DMSO) δ 12.45 (s, 1H), 8.62 (s, 1H), 8.52 (d, J = 1.7 Hz, 2H), 8.36 (s, 1H), 8.30 (s, 1H), 8.26 (d, J = 1.6 Hz, 2H), 8.24 (s, 1H), 7.50 (ddd, J = 8.5, 7.2, 1.5 Hz, 1H), 7.46 – 7.38 (m, 2H), 7.37 – 7.27 (m, 2H), 7.14 (dd, J = 8.3, 1.2 Hz, 1H), 6.98 (ddd, J = 8.4, 7.2, 1.3 Hz, 1H), 6.85 (dd, J = 8.3, 1.5 Hz, 1H), 3.69 (s, 2H). Compound RD-2.1 ((E)-1-(4-isobutylphenyl)-3-phenylprop-2-en-1-one): A 500 mL recover flask was charged with a stir bar. To the flask was added 1-(4- isobutylphenyl)ethan-1-one (19.57 mmol, 3.540 g) and benzaldehyde (19.57 mmol, 2.077 g). To the flask was added 200 proof ethanol (10 mL) and the solution stirred to get a clear solution. To the flask was added water (4.70 mL), followed by 5N NaOH / water (23.48 mmol, 4.70 mL). The mixture was stirred at room temperature for 24 hours. The reaction mixture was diluted with water (~100 mL) and the resulting precipitate filtered off, washing with water. The crude solid was dried in vacuo overnight at room temperature to give an off-white solid, 4.844 g (94% yield). MS (APCI): calculated for Chemical Formula: C19H20O (M+H) = 265; found: 265.1H NMR (400 MHz, TCE) δ 7.99 – 7.92 (m, 2H), 7.80 (d, J = 15.7 Hz, 1H), 7.71 – 7.64 (m, 2H), 7.56 (d, J = 15.7 Hz, 1H), 7.45 (p, J = 3.5 Hz, 3H), 7.34 – 7.28 (m, 2H), 2.57 (d, J = 7.2 Hz, 2H), 1.92 (hept, J = 6.8 Hz, 1H), 0.93 (d, J = 6.6 Hz, 6H). Compound RD-2.3 (1-(4-isobutylphenyl)-4-nitro-3-phenylbutan-1-one): A 500 mL recovery flask was charged with Compound RD-2.2 (18.323 mmol, 4.844 g) and a stir bar. To the flask was added nitromethane (15 mL) and 200 proof ethanol (15 mL). The mixture was stirred to give a clear solution, then KOH (2.346 mmol, 137 mg) was added. A finned condenser was added, and the reaction mixture heated in an aluminum heat block at 95 °C for two hours. The crude reaction mixture was partitioned with EtOAc (~125 mL) and water (~125 mL). The layers were separated, the organic layer washed with water (1 X 50 mL), dried over MgSO4, filtered, and evaporated to dryness in vacuo to give a brown oil (which solidified very slowly at room temperature), 5.753 g (97% yield). MS (APCI): calculated for Chemical Formula: C20H23NO3(M+H) = 326; found: 326.1H NMR (400 MHz, TCE) δ 7.87 – 7.80 (m, 2H), 7.41 – 7.33 (m, 2H), 7.33 – 7.27 (m, 3H), 7.25 (d, J = 8.2 Hz, 2H), 4.85 (dd, J = 12.5, 6.3 Hz, 1H), 4.69 (dd, J = 12.5, 8.4 Hz, 1H), 4.20 (tt, J = 8.2, 6.2 Hz, 1H), 3.47 (dd, J = 17.9, 6.1 Hz, 1H), 3.39 (dd, J = 17.9, 7.8 Hz, 1H), 2.53 (d, J = 7.2 Hz, 2H), 1.89 (hept, J = 6.8 Hz, 1H), 0.90 (d, J = 6.6 Hz, 6H). Compound RD-2.5 (2-(4-isobutylphenyl)-4-phenyl-1H-pyrrole) (1655-52): A 500 mL recovery flask was charged with a stir bar. The system was flushed with argon. To the flask was added Compound RD-2.3 (17.670 mmol, 5.570 g), dry THF (200 mL), and dry methanol (100 mL). The reaction mixture was stirred at room temperature to get a clear solution. To the flask was added KOH (45.765 mmol, 2.568 g) and the reaction mixture stirred at room temperature for one hour. A 1L 2N round bottom flask was charged with a stir bar and fitted with a flow control, addition funnel, and gas adapter. The system was flushed with argon. To the flask was added dry MeOH (100 mL) and the reaction cooled to 0 °C. To this flask was carefully added 96% H2SO4(22 mL) (exothermic). Once the reaction had cooled back to 0 °C, the first solution was transferred to the addition funnel and added to the MeOH / H2SO4mixture over a period of 30 minutes. The mixture was stirred at 0 °C for 30 minutes, then at room temperature for two hours. The reaction mixture was poured into ~250 mL of crushed ice and diluted with EtOAc (~100 mL). The mixture was transferred to a separatory funnel and the emulsion broken by adding some NaCl. The layers were separated, the aqueous layer extracted with EtOAc (1 X 100 mL), the combined organic layer washed with brine (1 X 50 mL), dried over MgSO4, filtered, and evaporated to give a brown oil. This oil was transferred to a 500 mL recovery flask and a stir bar was added. To the flask was added ammonium acetate (85.88 mmol, 6.619 g), followed by acetic acid (30 mL). To the flask was added a finned condenser and the reaction mixture stirred and heated at 100 °C in an aluminum heat block overnight. The mixture was cooled to room temperature and diluted with water (~200 mL). The resulting precipitate was filtered off, washing with water. The precipitate was dissolved in DCM, separated from water, dried over MgSO4, filtered, and evaporated onto ~60g of flash silica gel in vacuo. This silica gel was transferred to a loader and purified by flash chromatography on silica gel (120g, equilibrate 0% EtOAc / hexanes, eluting 0% (2 CV) → 20% EtOAc / hexanes (20 CV)). Fractions containing product were evaporated to dryness in vacuo to give a blue-purplish solid, 2.981 g (61% yield from Compound 59.2). MS (APCI): calculated for Chemical Formula: C20H21N (M+H) = 276; found: 276.1H NMR (400 MHz, TCE) δ 8.51 (s, 1H), 7.61 – 7.55 (m, 2H), 7.48 – 7.42 (m, 2H), 7.38 (t, J = 7.7 Hz, 2H), 7.26 – 7.17 (m, 3H), 7.16 (dd, J = 2.7, 1.7 Hz, 1H), 6.80 (dd, J = 2.8, 1.7 Hz, 1H), 2.50 (d, J = 7.2 Hz, 2H), 1.89 (hept, J = 6.8 Hz, 1H), 0.93 (d, J = 6.6 Hz, 6H). Compound RD-2.6 (4-(5,5-difluoro-3,7-bis(4-isobutylphenyl)-1,9-diphenyl-5H- 4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinin-10-yl)-3,5-dimethylphenol) (1655- 56): Compound RD-2.6 was synthesized from Compound RD-2.5 (2.00 mmol, 551 mg), and 4-hydroxy-2,6-dimethylbenzaldehyde (1.00 mmol, 150 mg), and pTsOH.H2O (0.300 mmol, 57 mg), then DDQ (1.70 mmol, 386 mg) and 2X Et3N (8.000 mmol,1.12 mL) and BF3.OEt2(12.00 mmol, 1.48 mL) in dry DCE (50 mL) at 60 °C, then 50 °C. The crude reaction mixture was diluted with ~10 mL of hexanes and loaded onto ~30g of flash silica gel in a loader and purified by flash chromatography on silica gel (120g, equilibrate 0% EtOAc / hexanes, eluting 0% (2 CV) → 20% EtOAc / hexanes (20 CV)). Fractions containing product were evaporated to dryness in vacuo to give a deep red solid, 219 mg (30% yield). MS (APCI): calculated for Chemical Formula: C49H47BF2N2O (M+H) = 729; found: 729.1H NMR (400 MHz, TCE) δ 7.87 (d, J = 8.1 Hz, 4H), 7.26 (d, J = 8.2 Hz, 4H), 7.05 – 6.98 (m, 2H), 6.98 – 6.89 (m, 4H), 6.83 – 6.75 (m, 4H), 6.50 (s, 2H), 5.70 (s, 2H), 4.19 (s, 1H), 2.55 (d, J = 7.1 Hz, 4H), 2.03 – 1.84 (m, 8H), 0.94 (d, J = 6.6 Hz, 12H). Compound RD-2 (4-(5,5-difluoro-3,7-bis(4-isobutylphenyl)-1,9-diphenyl-5H-4l4,5l4- dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinin-10-yl)-3,5-dimethylphenyl 2-(4-(5,11- bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin- 2(3H)-yl)phenyl)acetate): Compound RD-1 was synthesized from Compound FD-4.3 (0.0823 mmol, 70 mg), Compound RD-2.6 (0.0549 mmol, 40 mg), DMAP.pTsOH salt (0.110 mmol, 32 mg), and EDC.HCl (0.192 mmol, 37 mg) in dry DCM (10 mL) in a manner similar to Compound RD- 2.2. The crude reaction mixture was diluted with hexanes and loaded onto ~20g of flash silica gel in a loader and purified by flash chromatography on silica gel (120g, equilibrate 0% EtOAc / DCM, eluting isocratic 0%). Fractions containing product were evaporated to dryness in vacuo to give a deep red solid, 62 mg (73% yield). MS (APCI): calculated for Chemical Formula: C91H64BF14N3O5(M+H) = 1556; found: 1556.1H NMR (400 MHz, TCE) δ 8.78 (s, 1H), 8.52 (s, 1H), 8.32 – 8.24 (m, 2H), 8.08 (s, 1H), 8.03 (s, 3H), 7.88 (d, J = 8.0 Hz, 4H), 7.60 (d, J = 8.3 Hz, 2H), 7.49 (ddd, J = 8.5, 6.1, 2.7 Hz, 1H), 7.41 (d, J = 8.3 Hz, 2H), 7.27 (dd, J = 7.8, 4.7 Hz, 5H), 7.07 – 6.88 (m, 8H), 6.78 (dt, J = 6.7, 1.5 Hz, 4H), 6.51 (s, 2H), 6.09 (s, 2H), 3.90 (s, 2H), 2.55 (d, J = 7.1 Hz, 4H), 2.05 (s, 6H), 1.92 (hept, J = 6.6 Hz, 2H), 0.95 (d, J = 6.6 Hz, 12H). Synthesis Procedure of Compound RD-3 General procedure of Compound RD-3.2 synthesis— 4-(3,7-bis(4-bromophenyl)- 5,5-difluoro-1,9-diphenyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinin-10- yl)-3,5-dimethylphenol: A 100 mL 2 neck round bottomed flask was fitted with an air condenser and a stir bar. To the flask, RD-3.1 (synthesized according to literature: Synlett, 2016, 27(11), 1738-1742); (1.0 g, 3.35 mmol) and 4-hydroxyl-2,6-dimethylbenzaldehyde (251.9 mg, 1.68 mmol) were added, followed by anhydrous dichloroethane (35 ml). The reaction mixture was sparged with Ar for 30 minutes, then p-TsOH•H2O (57.3 mg, 0.30 mmol) was added. The reaction solution was heated up to 60 °C and kept at this temperature overnight. Then the reaction was cooled down to room temperature and DDQ (608.4 mg, 2.68 mmol) was added. The reaction was kept at room temperature for 30 minutes. Then BF3•OEt2(2.5 mL, 20.1 mmol) and Et3N (1.9 mL, 13.4 mmol) were added at room temperature. The reaction mixture was heated up to 50 °C and kept at this temperature for 2 hours. The reaction mixture was loaded with silica gel and purified by flash chromatography, using DCM in Hexane (0-100%) as an eluant to provide the pure RD-3.2 as a dark purple to golden solid, 560.0 mg, 43% yield. MS (APCI): calculated for Chemical Formula: C41H29BBr2F2N2O ([M-H]-) = 774 found: 774.1H NMR (400 MHz, CDCl2CDCl2) 7.81 (m, 4H), 7.62 (m, 4H), 7.02 (m, 2H), 6.95 (m, 4H), 6.78 (m, 4H), 6.47 (s, 2H), 5.71 (s, 2H), 4.27 (s, 1H), 1.98 (s, 6H). General procedure of Compound RD-3.3 synthesis— 3,3'-((5,5-difluoro-10-(4- hydroxy-2,6-dimethylphenyl)-1,9-diphenyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'- f][1,3,2]diazaborinine-3,7-diyl)bis(4,1-phenylene))bis(prop-2-yn-1-ol): A 100 mL Schlenk tube was fitted with a stir bar. To the tube, RD-3.2 (155.0 mg, 0.20 mmol), CuI (7.6 mg, 0.04 mmol), PdCl2(PPh3)2(28.1 mg, 0.04 mmol) and prop-2-yn-1-ol (44.8 mg, 0.8 mmol) were added, followed by anhydrous Et3N (5 ml). The reaction mixture was sparged with N2for 30 minutes. The reaction mixture was heated up to 80 °C and kept at this temperature for 8 hours. LCMS showed the completion of the reaction. DCM (50 ml) and 0.5 M HCl (100 mL) were added. The aqueous phase was further extracted with DCM (50 ml *3). The combined organic phase was concentrated under rotavapor, and the crude was purified by flash chromatography, using EtOAc in DCM (0-50%) as an eluant to provide the pure RD-3.3 as a dark purple solid, 111.0 mg, 77% yield. MS (APCI): calculated for Chemical Formula: C47H35BF2N2O3([M-H]-) = 724 found: 724.1H NMR (400 MHz, CDCl2CDCl2) 7.92 (m, 4H), 7.55 (m, 4H), 7.02 (m, 2H), 6.94 (m, 4H), 6.79 (m, 4H), 6.51 (s, 2H), 5.71 (s, 2H), 4.54 (d, J = 6.0 Hz, 4H), 4.27 (s, 1H), 1.98 (s, 6H), 1.77 (t, J = 6.0 Hz, 2H). General procedure of Compound RD-3 synthesis— ((10-(4-(2-(4-(5,11-bis(3,5- bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)- yl)phenyl)acetoxy)-2,6-dimethylphenyl)-5,5-difluoro-1,9-diphenyl-5H-4l4,5l4- dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-3,7-diyl)bis(4,1-phenylene))bis(prop-2- yne-3,1-diyl) bis(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H- xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate): A 25 mL vial was fitted with a stir bar. To the vial, Compound RD-3.3 (50.0 mg, 0.07 mmol), FD-4.3 (355.8 mg, 0.42 mmol), DIC (123.5 mg, 0.98 mmol) and DMAP (38.0 mg, 0.32 mmol) were added, followed by anhydrous DCM (11 ml). The reaction mixture was kept at room temperature overnight. The reaction mixture was loaded with silica gel and purified by flash chromatography, using EtOAc in DCM (0-10%) as the eluant to provide RD-3 as a dark purple red solid. The solid was further triturated with EtOAc / MeOH (2 ml / 10 ml) to deliver RD-3. The solid was further purified by flash chromatography using EtOAc in Hexane (0-60%) and EtOAc in DCM (0-10%) as the eluants, then triturated with DCM / EtOAc / MeOH (9:1:10), and the cycle was repeated twice, to provide pure RD-3. 163.0 mg, 73% yield.1H NMR (400 MHz, CDCl2CDCl2) 8.77 (s, 1H), 8.73 (s, 2H), 8.52 (s, 1H), 8.50 (s, 2H), 8.26 (m, 6H), 8.04 (m, 12H), 7.92 (m, 4H), 7.58 (m, 10H), 7.48 (m, 3H), 7.40 (m, 2H), 7.34 (m, 4H), 7.27 (m, 3H), 6.99 (m, 12H), 6.76 (m, 4H), 6.51 (s, 2H), 6.10 (s, 2H), 5.01 (s, 4H), 3.90 (s, 2H), 3.85 (s, 4H), 2.04 (s, 6H). Additional Synthesis of RD-3

[0057] Compound 9.1 (5,11-dibromo-1H,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. To the flask was added 1H,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), followed by ortho-dichlorobenzene (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 with an aluminum heat block 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 to give orangish solids, 10.866 g total (69.9% yield). Both had similar LCMS and NMR. MS (APCI): calculated for Chemical Formula: C18H6Br2O4(M+H) = 445; found: 445.1H NMR (400 MHz, TCE) δ 9.47 (dd, J = 8.4, 1.5 Hz, 1H), 8.76 (d, J = 14.2 Hz, 2H), 7.72 – 7.63 (m, 1H), 7.56 (dd, J = 8.3, 1.4 Hz, 1H), 7.46 (ddd, J = 8.5, 6.7, 1.9 Hz, 1H). Compound 9.2 (2-(4-(5,11-dibromo-1,3-dioxo-1H-xantheno[2,1,9- def]isoquinolin- 2(3H)-yl)phenyl)acetic acid): Compound 82.1 (1655-19) was synthesized from Compound (9.1) (7.000 mmol, 3.136 g), 2-(4- aminophenyl)acetic acid (14.00 mmol, 2.117 g), and DMAP (2.100 mmol, 257 mg) in anhydrous DMF (65 mL) at 160 °C in a manner similar to Compound 32.1. The crude reaction mixture was cooled to 0 °C and quenched with 6N HCl (~5 mL) and diluted with water (up to ~350 mL). The precipitate was filtered off, washing with water. The product (10.2) was dried by suction and used without further purification in the next reactions. Assume 100% yield. MS (APCI): calculated for Chemical Formula: C26H13Br2NO5(M+H) = 578; found: 578. Compound 9.3 (2-(4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H- xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid): Compound 9.3 was synthesized from Compound 9.2 (3.500 mmol, 2.034 g), (4- (trifluoromethyl)phenyl)boronic acid (14.00 mmol, 2.659 g), K2CO3(19.25 mmol, 2.661 g), and Pd(dppf)Cl2(0.0245 mmol, 179 mg) in THF ( / 60 mL), DMF (12 mL), and water (6 mL) with heating at 80 °C under argon atmosphere overnight. The crude reaction mixture was evaporated to dryness in vacuo, taken up in DCM, and evaporated in vacuo onto ~35 g of flash silica gel and purified by flash chromatography on silica gel (220g, equilibrate 0% EtOAc / DCM, eluting 0% (10 CV) to 15.3% EtOAc / DCM (15.3 CV) to 40% EtOAc / DCM (10 CV) to isocratic 40% EtOAc / DCM). EtOAc contains 0.1% v / v TFA. Fractions containing product were evaporated to dryness in vacuo to give a brown-yellow solid, 2.000 g (80.3% from Compound 80.1 (1655-11)). MS (APCI): calculated for Chemical Formula: C40H21F6NO5(M+H) = 710; found: 710.1H NMR (400 MHz, DMSO) δ 12.44 (s, 1H), 8.47 (s, 1H), 8.23 (s, 1H), 8.02 (d, J = 8.1 Hz, 2H), 7.97 – 7.88 (m, 4H), 7.75 (d, J = 8.0 Hz, 2H), 7.49 – 7.37 (m, 3H), 7.31 (d, J = 8.2 Hz, 1H), 7.30 – 7.24 (m, 2H), 7.02 – 6.91 (m, 2H), 3.68 (s, 2H).

[0058] Scheme of compound 11 synthesis General procedure of compound 11.1 synthesis— 4-(3,7-bis(4-bromophenyl)-5,5- difluoro-1,9-diphenyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinin-10-yl)- 3,5-dimethylphenol: A 100 mL 2 neck round bottomed flask was fitted with an air condenser and a stir bar. To the flask, 2-(4-bromophenyl)-4-phenyl-1H-pyrrole (1.0 g, 3.35 mmol) and 4-hydroxyl-2,6-dimethylbenzaldehyde (251.9 mg, 1.68 mmol) were added, followed by anhydrous dichloroethane (35 ml). The reaction mixture was sparged with Ar for 30 minutes, then p-TsOH•H2O (57.3 mg, 0.30 mmol) was added. The reaction solution was heated up to 60 °C and kept at this temperature overnight. Then the reaction was cooled down to room temperature and DDQ (608.4 mg, 2.68 mmol) was added. The reaction was kept at room temperature for 30 minutes. Then BF3•OEt2(2.5 mL, 20.1 mmol) and Et3N (1.9 mL, 13.4 mmol) were added at room temperature. The reaction mixture was heated up to 50 °C and kept at this temperature for 2 hours. The reaction mixture was loaded with silica gel and purified by flash chromatography, using DCM in Hexane (0-100%) as an eluant to provide the pure 12,1 as a dark purple to golden solid, 560.0 mg, 43% yield. MS (APCI): calculated for Chemical Formula: C41H29BBr2F2N2O ([M- H]-) = 774 found: 774.1H NMR (400 MHz, CDCl2CDCl2) 7.81 (m, 4H), 7.62 (m, 4H), 7.02 (m, 2H), 6.95 (m, 4H), 6.78 (m, 4H), 6.47 (s, 2H), 5.71 (s, 2H), 4.27 (s, 1H), 1.98 (s, 6H). General procedure of compound 11.2 synthesis— 3,3'-((5,5-difluoro-10-(4-hydroxy- 2,6-dimethylphenyl)-1,9-diphenyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'- f][1,3,2]diazaborinine-3,7-diyl)bis(4,1-phenylene))bis(prop-2-yn-1-ol): A 100 mL Schlenk tube was fitted with a stir bar. To the tube, Compound 11.1 (155.0 mg, 0.20 mmol), CuI (7.6 mg, 0.04 mmol), PdCl2(PPh3)2(28.1 mg, 0.04 mmol) and prop-2-yn-1-ol (44.8 mg, 0.8 mmol) were added, followed by anhydrous Et3N (5 ml). The reaction mixture was sparged with N2for 30 minutes. The reaction mixture was heated up to 80 °C and kept at this temperature for 8 hours. LCMS showed completion of the reaction. DCM (50 ml) and 0.5 M HCl (100 mL) were added. The aqueous phase was further extracted with DCM (50 ml *3). The combined organic phase was concentrated under rotovapor, and the crude was purified by flash chromatography, using EtOAc in DCM (0-50%) as an eluant to provide the pure 12.2 as a dark purple solid, 111.0 mg, 77% yield. MS (APCI): calculated for Chemical Formula: C47H35BF2N2O3([M-H]-) = 724 found: 724.1H NMR (400 MHz, CDCl2CDCl2) 7.92 (m, 4H), 7.55 (m, 4H), 7.02 (m, 2H), 6.94 (m, 4H), 6.79 (m, 4H), 6.51 (s, 2H), 5.71 (s, 2H), 4.54 (d, J = 6.0 Hz, 4H), 4.27 (s, 1H), 1.98 (s, 6H), 1.77 (t, J = 6.0 Hz, 2H). Scheme of Compound RD-3 synthesis General procedure of Compound RD-3 synthesis— ((10-(4-(2-(4-(1,3-dioxo-5,11- bis(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)- yl)phenyl)acetoxy)-2,6-dimethylphenyl)-5,5-difluoro-1,9-diphenyl-5H-4l4,5l4- dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-3,7-diyl)bis(4,1-phenylene))bis(prop-2- yne-3,1-diyl) bis(2-(4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H- xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate): A 25 mL vial was fitted with a stir bar. To the vial, Compound 12.1 (50.0 mg, 0.07 mmol), Compound 9.3 (261.5 mg, 0.42 mmol), DIC (123.5 mg, 0.98 mmol) and DMAP (38.0 mg, 0.32 mmol) were added, followed by anhydrous DCM (11 ml). The reaction mixture was kept at room temperature overnight. The reaction mixture was loaded with silica gel and purified by flash chromatography, using EtOAc in DCM (0 to 10%) as the eluant to provide RD-3 as a dark purple red solid. The solid was further triturated with EtOAc / MeOH (2 ml / 10 ml) to deliver RD-3. The solid was further purified by flash chromatography using EtOAc in Hexane (0 to 60%) and EtOAc in DCM (0 to 10%) as the eluants, then triturated with DCM / EtOAc / MeOH (10:1:10), and the cycle was repeated twice, to provide pure RD-3. 139.0 mg, 71% yield.1H NMR (400 MHz, CDCl2CDCl2) 8.72 (s, 1H), 8.69 (s, 2H), 8.49 (s, 1H), 8.46 (s, 2H), 7.87 (m, 22H), 7.62 (m, 16H), 7.41 (m, 5H), 7.31 (m, 7H), 7.00 (m, 12H), 6.76 (m, 4H), 6.51 (s, 2H), 6.10 (s, 2H), 5.01 (s, 4H), 3.90 (s, 2H), 3.85 (s, 4H), 2.04 (s, 6H). Synthesis of Compound RD-4: Compound RD-4.1: To a solution of 3-trifluoromethylbenzaldehyde (870mg, 5 mmol), 4-bromoacetophenone (995mg, 5 mmol) in 10 mL ethanol, a 10% sodium hydroxide aqueous solution (5 mL) was added dropwise. A white precipitate formed after one minute. The mixture was stirred for 15 min, filtered and washed with 20 mL ethanol / water (1:1) to give a white solid (1.53 g, in 86.2% yield). LCMS (APCI-): Calcd for C16H10BrF3O: 353.99: found: 354.1H NMR (400 MHz, d2-TCE) δ 7.86 – 7.78 (m, 3H), 7.77 – 7.68 (m, 2H), 7.66 – 7.57 (m, 3H), 7.53 – 7.47 (m, 1H), 7.43 (d, J = 15.7 Hz, 1H). Compound RD-4.2: To a solution of compound RD-4.1 (0.9 g, 2.5 mmol) in 10 mL ethanol, nitromethane (3 mL, 43 mmol) was added, then potassium hydroxide pellet (28 mg, 0.5 mmol). The mixture was stirred at 90 °C for 30 min under inert atmosphere. LCMS analysis indicated that starting material was consumed completely. To the solution, 50 mL of water was added and the aqueous solution was extracted with EA (50 mL x 2). The organic phase was collected, loaded on silica gel and purified by flash chromatography using eluents of hexanes / DCM (0% → 50% DCM). The main peak was collected, and after removal of solvent under reduced pressure, a colorless liquid was obtained (0.9 g, in 86% yield). LCMA (APCI+): Calcd for C17H14BrF3NO3(M+H): 416.0; found: 416.1H NMR (400 MHz, d2-TCE) δ 7.73 – 7.65 (m, 2H), 7.59 – 7.52 (m, 2H), 7.49 (dt, J = 5.0, 2.4 Hz, 1H), 7.46 – 7.39 (m, 3H), 4.78 (dd, J = 12.8, 6.3 Hz, 1H), 4.63 (dd, J = 12.8, 8.3 Hz, 1H), 4.19 (dd, J = 8.3, 6.6 Hz, 1H), 3.34 (d, J = 6.8 Hz, 2H). Compound RD-4.3: To a solution of compound RD-4.2 (5.7g, 13 mmol) in THF / methanol (100 mL / 60 mL), KOH (1.46 g, 26 mmol) was added at 0 °C. The mixture was stirred for 10 min, then transferred into an addition funnel. This solution was added dropwise into a solution of Conc. H2SO4(15 mL) in methanol (60 mL) at 0 °C over a period of one hour. The resulting solution was stirred at 0 °C for an additional one hour, then poured into 300 g of ice slowly with stirring. The mixture was extracted with ethyl acetate (200 mL x2). The organic phase was washed with 200 mL 10% K2CO3aqueous solution, then washed with 150 mL brine, and dried over MgSO4. After filtration, the solution was concentrated to give a yellow liquid (5.3g, in 94% yield). LCMS (APCI-): calcd for C19H17BrF3O3(M-H): 429.0; Found: 429.1H NMR (400 MHz, d2-TCE) δ 7.73 – 7.67 (m, 2H), 7.54 – 7.32 (m, 6H), 4.34 (d, J = 5.1 Hz, 1H), 4.01 (q, J = 7.1 Hz, 1H), 3.67 (dt, J = 8.4, 5.0 Hz, 1H), 3.57 – 3.41 (m, 2H), 3.27 (s, 3H), 3.22 (s, 3H), 3.20 (m, 1H). Compound RD-4.4: A mixture of compound RD-4.3 (3.0 g, 6.98 mmol) and ammonium acetate (2.5 g, 32.4 mmol) in 15 mL acetic acid was heated at 100 °C under argon for 5 hours. The mixture was worked up with water / ethyl acetate (200 mL). The organic phase was collected and washed with brine, and concentrated under reduced pressure to give a greenish solid (2.55 g), which was washed with hexanes and dried in air to give a solid (2.23 g, in 91% yield). LCMS (APCI+): Calcd for C17H12BrF3N (M+H): 366.0; Found: 366.1H NMR (400 MHz, d2-TCE) δ 8.53 (s, 1H), 7.69 (d, J = 1.7 Hz, 1H), 7.66 (dt, J = 7.1, 1.9 Hz, 1H), 7.50 – 7.44 (m, 2H), 7.44 – 7.36 (m, 2H), 7.36 – 7.29 (m, 2H), 7.15 (dd, J = 2.8, 1.7 Hz, 1H), 6.76 (dd, J = 2.8, 1.7 Hz, 1H). Compound RD-4: To a mixture of compound RD-4.4 (0.50 g, 1.36 mmol) and 2,4,6-trimethylbenzaldehyde (0.101 g, 0.68 mmol) in 25 mL DCE, p-TsOH (0.05g) was added and stirred at 60 °C under argon atmosphere for 24 hours. The solution was cooled to room temperature, then DDQ (0.17g, 0.75 mmol) was added into this solution and stirred for one hour. To the resulting mixture, at 0 °C, TEA (0.5 mL, 3.5 mmol) and BF3-Et2O (1.5 mL, 12.4 mmol) were added at 0 °C. Then the mixture was stirred at 50 °C for one hour, then at room temperature overnight. The resulting mixture was passed through a silica gel column using eluents of hexanes / DCM (0% → 50% DCM). The main fraction was collected, concentrated and loaded on silica gel, purified by flash chromatography using eluents of hexanes / DCM (0% → 50% DCM). The desired peak was collected, and removal of solvents gave a dark purple solid (316 mg, in 51% yield). LCMS (APCI-): Calcd for C44H29BBr2F8N2: 906.07; Found: 9061H NMR (400 MHz, d2-TCE) δ 7.96 (d, J = 7.9 Hz, 4H), 7.56 (d, J = 58.7 Hz, 8H), 7.33 – 6.76 (m, 32H), 6.50 (s, 2H), 5.94 (s, 2H), 1.94 (s, 6H), 1.72 (s, 3H).

[0059] Synthesis of Compound RD-5: Compound RD-5: To a solution of compound RD-5.1 (91 mg, 0.1 mmol) in 5 mL anhydrous toluene, 0.2 mL of 1M solution of BCl3 in toluene was added, followed by the addition of 0.186g TMS-TFA (trimethylsilyl trifluoroacetate). The mixture was stirred at room temperature for 3 hours. The mixture was diluted with 25 mL toluene and washed with brine (50mL x 2), and the organic phase was collected, loaded on silica gel, and then purified by flash chromatography, using eluents of hexanes / DCM (0% DCM to 30% DCM) twice. Removal of solvents gave a red solid (80 mg, in 73% yield). LCMS (APCI-): Calcd for C48H29BBr2F12N2O4= 1094.04; found: 1094. 1H NMR (400 MHz, TCE) δ 7.56 – 7.49 (m, 4H), 7.44 – 7.36 (m, 4H), 7.16 (d, J = 7.3 Hz, 2H), 7.09 – 6.98 (m, 4H), 6.91 (s, 2H), 6.38 (s, 2H), 5.95 (s, 2H), 1.99 (s, 6H), 1.71 (s, 3H).

[0060] Synthesis of Compound RD-6: Compound RD-6.1 ((E)-3-(3,5-bis(trifluoromethyl)phenyl)-1-(4-bromophenyl)prop- 2-en-1-one): Compound RD-6.1 was synthesized from (E)-3-(3,5- bis(trifluoromethyl)phenyl)-1-(4-bromophenyl)prop-2-en-1-one (100.0 mmol, 19900 mg), 3,5-bis(trifluoromethyl)benzaldehyde (100.0 mmol, 16.5 mL), and NaOH (250.0 mmol, 10000 mg) in a manner similar to Compound 1814-58. Workup was similar as well to give a light yellow solid, assume 100% yield (42315 mg). MS (APCI): calculated for Chemical Formula: C17H9BrF6O (M+H) 423; found: 423. NMR shows ~70-80% purity. Used as-is in the next step. Compound RD-6.2 (3-(3,5-bis(trifluoromethyl)phenyl)-1-(4-bromophenyl)-4- nitrobutan-1-one): Compound RD-6.2 was synthesized from Compound RD-6.1(assume 100%, 100.0 mmol, 42315 mg), nitromethane (1200 mmol, 64.4 mL), and KOH (10.00 mmol, 561 mg) in 200 proof ethanol (150 mL) at 70 ℃ for one hour. The workup was similar as well. It was evaporated onto ~40g of flash silica gel in vacuo and purified by flash chromatography on silica gel (220g, 0% DCM / hexanes (2 CV) → 60% (10 CV) → 80% (0 CV) → 80% isocratic)). Fractions containing product were evaporated to dryness in vacuo to give a yellow-orange oil, 27830 mg (58% yield over 2 steps). MS (APCI): calculated for Chemical Formula: C18H12BrF6NO3(M+H) 484; found: 484.1H NMR (400 MHz, CDCl3) δ 7.83 – 7.74 (m, 5H), 7.66 – 7.58 (m, 2H), 4.88 (dd, J = 13.1, 6.3 Hz, 1H), 4.75 (dd, J = 13.0, 8.0 Hz, 1H), 4.48 – 4.30 (m, 1H), 3.47 (t, J = 7.0 Hz, 2H). Compound RD-6.3 (3-(3,5-bis(trifluoromethyl)phenyl)-1-(4-bromophenyl)-4,4- dimethoxybutan-1-one): Compound RD-6.3 was synthesized from Compound RD-6.2 (57.48 mmol, 27830 mg), KOH (115.0 mmol, 6450 mg) in dry THF / dry methanol (130 mL / 100 mL), then with 25 mL of 96% sulfuric acid in dry methanol (100 mL) in a manner similar to Compound 1814-61. The workup was similar and gave an orangish oil, 26220 mg (91% yield). MS (APCI): calculated for Chemical Formula: C20H17BrF6O3(M+H) 499; found: 499. Used as-is in the next step. Compound RD-6.4 (4-(3,5-bis(trifluoromethyl)phenyl)-2-(4-bromophenyl)-1H- pyrrole): Compound RD-6.4 was synthesized from Compound RD-6.3 (52.52 mmol, 26220 mg) and ammonium acetate (262.6 mmol, 20241 mg) in acetic acid (150 mL) in a manner similar to Compound 1814-62. The workup was similar. It was evaporated onto ~40g of flash silica gel in vacuo and purified by flash chromatography on silica gel (220g, 0% DCM / hexanes (2 CV) → 40% (10 CV)). Fractions containing product were evaporated to dryness in vacuo, triturated with hot hexanes, cooled to room temperature, filtered, and dried in vacuo to give a bluish solid, 4311 mg (19% yield). MS (APCI): calculated for Chemical Formula: C18H10BrF6N (M+H) 434; found: 434.1H NMR (400 MHz, TCE) δ 8.66 (s, 1H), 7.95 (s, 2H), 7.69 (s, 1H), 7.56 (d, J = 8.4 Hz, 2H), 7.47 – 7.39 (m, 2H), 7.29 (t, J = 2.4 Hz, 1H), 6.87 (t, J = 2.2 Hz, 1H). Compound RD-6.5 (1,9-bis(3,5-bis(trifluoromethyl)phenyl)-3,7-bis(4-bromophenyl)- 5,5-difluoro-10-mesityl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine): Compound RD-6.5 was synthesized from Compound RD-6.4 (4.000 mmol, 1374 mg), 2,4,6-trimethylbenzaldehyde (2.000 mmol, 0.29 mL), and pTsOH.H2O (0.2000 mmol, 38 mg) stirred in dry DCE (50 mL) at 60 °C for ~24 hours, cooled to room temperature, then treated with DDQ (4.000 mmol, 908 mg) and stirred at RT for 10 minutes, then treated with triethylamine (16.00 mmol, 2.2 mL) and BF3.OEt2(24.00 mmol, 3.0 mL). The triethylamine (16.00 mmol, 2.2 mL) and BF3.OEt2(24.00 mmol, 3.0 mL) treatment was repeated, and the mixture stirred for one hour at 60 °C. The mixture was poured into ~150 mL of saturated sodium bicarbonate solution, stirred for 10 minutes, filtered through a polypropylene frit to retain water, eluting with DCM, the DCM evaporated to dryness in vacuo, the residue evaporated onto ~45g of flash silica gel, packed into a loader, and purified by flash chromatography on silica gel (220g, 0% EtOAc / hexanes (2 CV) → 5% (10 CV), stop at 0.6%, 0.9%, 0.8%, 1.5%, isocratic at each step)). Fractions containing product were evaporated to dryness in vacuo to give a deep red solid, 1360 mg (65% yield). MS (APCI): calculated for Chemical Formula: C46H27BBr2F14N2(M+H) 1043; found: 1043.1H NMR (400 MHz, TCE) δ 7.88 – 7.78 (m, 4H), 7.70 – 7.61 (m, 4H), 7.49 (s, 2H), 7.28 (d, J = 1.7 Hz, 4H), 6.57 (s, 2H), 6.05 (s, 2H), 2.02 (s, 6H), 1.79 (s, 3H). Compound RD-6 (1,9-bis(3,5-bis(trifluoromethyl)phenyl)-3,7-bis(4-bromophenyl)- 10-mesityl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-5,5-diyl bis(2,2,2- trifluoroacetate)): Compound RD-6 was synthesized from Compound RD-6.5 (0.1000 mmol, 104 mg), trimethylsilyl 2,2,2-trifluoroacetate (3.000 mmol, 0.52 mL), BF3.OEt2(0.1500 mmol, 0.085 mL) and triethylamine (0.1000 mmol, 0.014 mL) in dry DCE (10 mL) at 50 °C for 120 minutes under argon, then cooled to room temperature and worked up in a manner similar to Compound 1814-26. The crude product was evaporated onto ~15g of flash silica gel and purified by flash chromatography on silica gel (40g, 0% EtOAc / hexanes (2 CV) → 5% (10 CV), stop at 2.7% isocratic)). Fractions containing product were evaporated to dryness in vacuo to give a deep red solid, 83 mg (68% yield). MS (APCI): calculated for Chemical Formula: C50H27BBr2F18N2O4(M+H) 1231; found: 1231.1H NMR (400 MHz, CDCl3) δ 7.66 – 7.58 (m, 4H), 7.47 (dd, J = 9.0, 2.4 Hz, 6H), 7.31 (d, J = 1.7 Hz, 4H), 6.49 (s, 2H), 6.06 (s, 2H), 2.09 (s, 6H), 1.78 (s, 3H). Compound 1806-69: Synthesis of Compound RD-7: Compound RD-7.2 (3,7-bis(4-(tert-butyl)phenyl)-5,5-difluoro-10-mesityl-1,9-bis(3- (trifluoromethyl)phenyl)-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine): Compound RD-7.2 was synthesized from Compound RD-7.1 (4.000 mmol, 1374 mg), 2,4,6-trimethylbenzaldehyde (2.000 mmol, 0.29 mL), and pTsOH.H2O (0.2000 mmol, 38 mg) stirred in dry DCE (50 mL) at 60 °C for ~24 hours, cooled to room temperature, then treated with DDQ (4.000 mmol, 908 mg) and stirred at RT for 10 minutes, then treated with triethylamine (16.00 mmol, 2.2 mL) and BF3.OEt2(24.00 mmol, 3.0 mL),. The triethylamine (16.00 mmol, 2.2 mL) and BF3.OEt2(24.00 mmol, 3.0 mL) treatment was repeated, and the mixture stirred for one hour at 60 °C. The mixture was poured into ~150 mL of saturated sodium bicarbonate solution, stirred for 10 minutes, filtered through a polypropylene frit to retain water, eluting with DCM, the DCM evaporated to dryness in vacuo, the residue evaporated onto ~45g of flash silica gel, packed into a loader, and purified by flash chromatography on silica gel (220g, 0% EtOAc / hexanes (2 CV) → 5% (10 CV), stop at 2.2%, 2.5%, isocratic at each step). Fractions containing product were evaporated to dryness in vacuo to give a reddish solid, 1125 mg (65% yield). MS (APCI): calculated for Chemical Formula: C52H47BF8N2(M+H) 863; found: 863.1H NMR (400 MHz, CDCl3) δ 7.98 – 7.77 (m, 4H), 7.61 – 7.41 (m, 4H), 7.23 – 7.15 (m, 2H), 7.05 (dd, J = 5.1, 1.4 Hz, 4H), 6.97 (s, 2H), 6.47 (s, 2H), 6.00 (s, 2H), 2.02 (s, 6H), 1.79 (s, 3H), 1.36 (s, 18H). Compound RD-7 (3,7-bis(4-(tert-butyl)phenyl)-10-mesityl-1,9-bis(3- (trifluoromethyl)phenyl)-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-5,5- diyl bis(2,2,2-trifluoroacetate)): Compound RD-7 was synthesized from Compound RD- 7.2 (0.5000 mmol, 431 mg), trimethylsilyl 2,2,2-trifluoroacetate (10.00 mmol, 1.7 mL), and BCl3(1.0M in toluene, 1.000 mmol, 1.0 mL) in a manner similar to Compound 1806-26. The reaction was worked up in a similar manner. The crude product was evaporated onto ~40g of flash silica gel in vacuo and purified by flash chromatography on silica gel (120g, 0% toluene / hexanes (2 CV) → 50% (15 CV), stop at 11.0%, 13.0%, 15.0%, 16.5%, isocratic at each step)). Fractions containing product were evaporated to dryness in vacuo to give a deep red solid, 125 mg (24% yield). MS (APCI): calculated for Chemical Formula: C56H47BF12N2O4(M+H) 1051; found: 1051.1H NMR (400 MHz, CDCl3) δ 7.61 – 7.54 (m, 4H), 7.49 – 7.41 (m, 4H), 7.21 (d, J = 7.6 Hz, 2H), 7.15 – 7.00 (m, 6H), 6.42 (s, 2H), 6.01 (s, 2H), 2.09 (s, 6H), 1.78 (s, 3H), 1.34 (s, 18H).

[0061] Synthesis of Compound RD-8: Compound RD-8.1 (2,6-diisopropylbenzaldehyde): 2-bromo-1,3-diisopropylbenzene (100.0 mmol, 20.6 mL) was dissolved in dry THF (150 mL) and cooled to -78 °C and treated with nBuLi solution (2.5M hexanes, 300.0 mmol, 120.0 mL) slowly over ~5 minutes with vigorous stirring. The reaction was stirred at -78 °C for 30 minutes, then treated with dry DMF (400.0 mmol, 30.8 mL), which was added slowly over ~5 minutes. The reaction mixture was allowed to warm slowly to room temperature over several hours, then quenched with saturated ammonium chloride solution. The reaction mixture was diluted with hexanes (300 mL) and the layers separated. The water layer was extracted with hexanes (1 X 200 mL), the combined organic layers dried over magnesium sulfate, filtered, and evaporated to dryness in vacuo. The mixture was taken up in hexanes and evaporated onto ~40g of flash silica and packed into a loader. It was purified by flash chromatography on silica gel (330g, 0% EtOAc / hexanes (2 CV) 10% (10 CV)). Fractions containing product were evaporated to dryness in vacuo to give a light greenish oil, 16.154g (84% yield). MS (APCI): calculated for Chemical Formula: C13H18O (M+H) 191; found: 191.1H NMR (400 MHz, TCE) δ 10.68 (s, 1H), 7.45 (t, J = 7.8 Hz, 1H), 7.26 (d, J = 7.8 Hz, 2H), 3.50 (hept, J = 6.8 Hz, 2H), 1.27 (d, J = 6.8 Hz, 12H). Compound RD-8 (3,7-bis(4-bromophenyl)-10-(2,6-diisopropylphenyl)-5,5-difluoro- 1,9-diphenyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine): Compound RD- 82 (6.000 mmol, 1789 mg), Compound RD-8.1 (3.000 mmol, 517 mg), and pTsOH.H2O (0.3000 mmol, 57 mg) were stirred at 60 °C under argon in dry DCE for 24 hours, then cooled to room temperature. The mixture was treated with DDQ (3.300 mmol, 749 mg), stirred at room temperature for 10 minutes, and then treated with triethylamine (24.00 mmol, 3.3 mL) and BF3.OEt2(36.00 mmol, 4.4 mL). The triethylamine (24.00 mmol, 3.3 mL) and BF3.OEt2(36.00 mmol, 4.4 mL) treatment was repeated, and the mixture stirred for one hour at 60 °C. The mixture was poured into ~200 mL of saturated sodium bicarbonate solution, stirred for 10 minutes, filtered through a polypropylene frit to retain water, eluting with DCM, the DCM evaporated to dryness in vacuo, the residue evaporated onto ~45g of flash silica gel, packed into a loader, and purified by flash chromatography on silica gel (120g, 0% DCM / hexanes (2 CV) → 40% (10 CV), stop at 4.8%, isocratic)). Fractions containing product were evaporated to dryness in vacuum then triturated with 1:1 MeOH:water, and dried in vacuo to give a deep red solid, 1145 mg (47% yield). MS (APCI): calculated for Chemical Formula: C45H37BBr2F2N2(M+H) 813; found: 813.1H NMR (400 MHz, CDCl3) δ 7.77 (d, J = 8.5 Hz, 3H), 7.57 (d, J = 8.5 Hz, 4H), 7.06 (t, J = 7.9 Hz, 1H), 7.03 – 6.96 (m, 2H), 6.89 (dd, J = 8.5, 6.9 Hz, 4H), 6.75 – 6.67 (m, 7H), 6.46 (s, 2H), 2.99 (hept, J = 6.8 Hz, 2H), 0.91 (d, J = 6.8 Hz, 12H). Synthesis of Compound RD-9: Compound RD-9.1 ((E)-1-(3-fluorophenyl)-3-(3-(trifluoromethyl)phenyl)prop-2-en-1- one): Compound RD-9.1 was synthesized from 1-(3-fluorophenyl)ethan-1-one (50.00 mmol, 6.1 mL), 3-(trifluoromethyl)benzaldehyde (50.00 mmol, 6.7 mL), and NaOH (125.0 mmol, 5000 mg). It was evaporated onto ~40g of flash silica gel and purified by flash chromatography on silica gel (220g, 0% DCM / hexanes (2 CV) → 10% (10 CV)). Fractions containing product were evaporated to dryness in vacuo to give a light yellow solid, 9906 mg (67% yield). MS (APCI): calculated for Chemical Formula: C16H10F4O (M+H) 295; found: 295.1H NMR (400 MHz, CDCl3) δ 7.89 (d, J = 2.0 Hz, 1H), 7.84 (d, J = 15.7 Hz, 1H), 7.81 (s, 2H), 7.72 (ddd, J = 9.4, 2.7, 1.6 Hz, 1H), 7.68 (dd, J = 8.1, 1.3 Hz, 1H), 7.53 (d, J = 15.7 Hz, 1H), 7.62 – 7.47 (m, 2H), 7.31 (tdd, J = 8.3, 2.7, 1.0 Hz, 1H). Compound RD-9.2 (1-(3-fluorophenyl)-4-nitro-3-(3-(trifluoromethyl)phenyl)butan-1- one): Compound RD-9.2 was synthesized from Compound RD-9.1 (23.76 mmol, 9660 mg), nitromethane (475.1 mmol, 25.5 mL), and KOH (4.751 mmol, 267 mL) in 200 proof ethanol (100 mL) in a manner similar to Compound 1814-60. The workup was accomplished in a similar manner. MS (APCI): calculated for Chemical Formula: C17H13F4NO3(M+H) 356; found: 356.1H NMR (400 MHz, CDCl3) δ 7.70 (dt, J = 7.7, 1.3 Hz, 1H), 7.63 – 7.41 (m, 7H), 7.29 (tdd, J = 8.3, 2.6, 1.0 Hz, 1H), 4.85 (dd, J = 12.8, 6.6 Hz, 1H), 4.72 (dd, J = 12.8, 7.9 Hz, 1H), 4.37 – 4.24 (m, 1H), 3.46 (d, J = 6.9 Hz, 2H). Used without further purification in the next step. Compound RD-9.3 (1-(3-fluorophenyl)-4,4-dimethoxy-3-(3- (trifluoromethyl)phenyl)butan-1-one): Compound RD-9.3 was synthesized from Compound RD-9.2 (23.76 mmol, 8440 mg), KOH (47.51 mmol, 2666 mg) in dry THF / dry methanol (130 / 100 mL, respectively), and 40 mL 96% sulfuric acid in 100 mL dry methanol in a manner similar to Compound 1814-61. The workup was accomplished in a similar manner to give an orangish oil, 8800 mg (100% yield). MS (APCI): calculated for Chemical Formula: C19H18F4O3(M+H) 371; found: 371. Used in next step as-is. Compound RD-9.4 (2-(3-fluorophenyl)-4-(3-(trifluoromethyl)phenyl)-1H-pyrrole): Compound RD-9.4 was synthesized from Compound RD-9.3 (assume 100%, 23.76 mmol, 8800 mg) and ammonium acetate (237.6 mmol, 18311 mg) in acetic acid (100 mL) in a manner similar to Compound 1814-62. The workup was accomplished in a similar manner. It was evaporated onto ~40g of flash silica gel in vacuo and purified by flash chromatography on silica gel (220g, 0% DCM / hexanes (2 CV) → 100% (10 CV) → 100% isocratic DCM)). Fractions containing product were evaporated to dryness in vacuo. The product was triturated with hot hexanes, cooled to room temperature, filtered, and dried in vacuo to give a bluish solid, 5357 mg (74% yield). MS (APCI): calculated for Chemical Formula: C17H11F4N (M+H) 306; found: 306.1H NMR (400 MHz, CDCl3) δ 8.49 (s, 1H), 7.78 (d, J = 2.1 Hz, 1H), 7.71 (dt, J = 6.4, 2.3 Hz, 1H), 7.56 – 7.41 (m, 2H), 7.35 (td, J = 8.0, 5.9 Hz, 1H), 7.28 (dt, J = 7.7, 1.3 Hz, 1H), 7.23 – 7.16 (m, 2H), 6.94 (tdd, J = 8.3, 2.5, 1.0 Hz, 1H), 6.84 (dd, J = 2.8, 1.7 Hz, 1H). Compound RD-9.5 (10-(2,6-dichlorophenyl)-5,5-difluoro-3,7-bis(3-fluorophenyl)- 1,9-bis(3-(trifluoromethyl)phenyl)-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'- f][1,3,2]diazaborinine): Compound RD-9.5 was synthesized from Compound RD-9.4 (4.000 mmol, 1221 mg), 2,6-dichlorobenzaldehyde (2.000 mmol, 350 mg), and pTsOH.H2O (0.2000 mmol, 38 mg) stirred in dry DCE (50 mL) at 40 °C for one hour, then treated with DDQ (2.600 mmol, 590 mg) and stirred at 40 °C for 10 minutes, then treated with triethylamine (16.00 mmol, 2.2 mL) and BF3.OEt2(24.00 mmol, 3.0 mL) The triethylamine (16.00 mmol, 2.2 mL) and BF3.OEt2(24.00 mmol, 3.0 mL) treatment was repeated, and the mixture stirred for one hour at 60 °C. The mixture was poured into ~150 mL of saturated sodium bicarbonate solution, stirred for 10 minutes, filtered through a polypropylene frit to retain water, eluting with DCM, the DCM evaporated to dryness in vacuo, the residue evaporated onto ~45g of flash silica gel, packed into a loader, and purified by flash chromatography on silica gel (220g, 0% toluene / hexanes (2 CV) → 35% (10 CV) → 35% isocratic)). Fractions containing product were evaporated to dryness in vacuo to give a deep red solid, 1214 mg (75% yield). MS (APCI): calculated for Chemical Formula: C41H21BCl2F10N2(M+H) 813; found: 813.1H NMR (400 MHz, CDCl3) δ 7.71 (dt, J = 7.9, 1.2 Hz, 2H), 7.66 (ddd, J = 9.9, 2.6, 1.6 Hz, 2H), 7.43 (td, J = 8.1, 5.9 Hz, 2H), 7.31 – 7.20 (m, 6H), 7.19 – 7.08 (m, 4H), 6.62 – 6.42 (m, 5H). Compound RD-9 (10-(2,6-dichlorophenyl)-3,7-bis(3-fluorophenyl)-1,9-bis(3- (trifluoromethyl)phenyl)-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-5,5- diyl bis(2,2,2-trifluoroacetate)): Compound RD-9 was synthesized from Compound RD- 9.5 (0.5000 mmol, 407 mg), trimethylsilyl 2,2,2-trifluoroacetate (10.00 mmol, 1.7 mL), and BCl3(1.0M in toluene, 1.000 mmol, 1.0 mL) in 50 mL dry toluene in a manner similar to Compound 1806-26. The reaction was worked up in a similar manner. The crude product was evaporated onto ~15g of flash silica gel in vacuo and purified by flash chromatography on silica gel (120g, 0% toluene / hexanes (2 CV) → 35% (10 CV), stop at 17.1%, 20.0%, 25.0%, 30.0%, 33.0%, isocratic at each step)). Fractions containing product were evaporated to dryness in vacuo to give a deep red solid, 424 mg (85% yield). MS (APCI): calculated for Chemical Formula: C45H21BCl2F14N2O4(M+H) 1001; found: 1001.1H NMR (400 MHz, CDCl3) δ 7.49 – 7.37 (m, 4H), 7.37 – 7.28 (m, 6H), 7.28 – 7.22 (m, 2H), 7.22 – 7.08 (m, 4H), 6.62 – 6.40 (m, 5H). Synthesis of Compound RD-10: Compound RD-10.1 (2,6-diisopropylbenzaldehyde): 2-bromo-1,3-diisopropylbenzene (100.0 mmol, 20.6 mL) was dissolved in dry THF (150 mL) and cooled to -78 °C and treated with nBuLi solution (2.5M hexanes, 300.0 mmol, 120.0 mL) slowly over ~5 minutes with vigorous stirring. The reaction was stirred at -78 °C for 30 minutes, then treated with dry DMF (400.0 mmol, 30.8 mL), added slowly over ~5 minutes. The reaction mixture was allowed to warm slowly to room temperature over several hours, then quenched with saturated ammonium chloride solution. The reaction mixture was diluted with hexanes (300 mL) and the layers separated. The water layer was extracted with hexanes (1 X 200 mL), the combined organic layers dried over magnesium sulfate, filtered, and evaporated to dryness in vacuo. The mixture was taken up in hexanes and evaporated onto ~40g of flash silica and packed into a loader. It was purified by flash chromatography on silica gel (330g, 0% EtOAc / hexanes (2 CV) → 10% (10 CV)). Fractions containing product were evaporated to dryness in vacuo to give a light greenish oil, 16.154g (84% yield). MS (APCI): calculated for Chemical Formula: C13H18O (M+H) 191; found: 191.1H NMR (400 MHz, TCE) δ 10.68 (s, 1H), 7.45 (t, J = 7.8 Hz, 1H), 7.26 (d, J = 7.8 Hz, 2H), 3.50 (hept, J = 6.8 Hz, 2H), 1.27 (d, J = 6.8 Hz, 12H). RD-10.2 (methyl 2-isopropyl-4-methyl-1H-pyrrole-3-carboxylate): methyl 4-methyl-3- oxopentanoate (100.0 mmol, 14.2 mL), aminoacetone hydrochloride (150.0 mmol, and 16.440 g), and NaOAc (200.0 mmol, 16.406 g) were stirred in acetic acid (100 mL) and water (100 mL) at 100 °C over the weekend under argon. The reaction mixture was cooled to room temperature and most of the solvents were evaporated in vacuo. The mixture was partitioned between DCM (200 mL) and water (50 mL). The remainder of acetic acid was carefully quenched with 10% K2CO3solution. The layers were separated, the aqueous layer was extracted with 2 X 50 mL DCM, and the combined organic layers were dried over magnesium sulfate, filtered, and evaporated to dryness in vacuo. The crude material was dissolved in a small amount of DCM and loaded onto ~50g of flash silica gel packed into a loader. it was purified by flash chromatography on silica gel (120g, 0% EtOAc / hexanes (2 CV) → 15% (15 CV)). Fractions containing product were evaporated to dryness in vacuo to give a light-yellow oil, 7.985 g (44% yield). MS (APCI): calculated for Chemical Formula: C10H15NO2(M+H) = 182; found: 182.1H NMR (400 MHz, acetic acid-d6) δ 9.96 (s, 1H), 6.40 (dq, J = 2.3, 1.1 Hz, 1H), 3.80 (dq, J = 14.1, 7.0 Hz, 1H), 2.16 (d, J = 1.1 Hz, 3H), 1.23 (d, J = 7.0 Hz, 6H). RD-10.3 (dimethyl 10-(2,6-diisopropylphenyl)-5,5-difluoro-3,7-diisopropyl-1,9- dimethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylate): Compound RD-10.2 (4.000 mmol, 725 mg), Compound RD-10.1 (2.000 mmol, 381 mg), and pTsOH.H2O (0.4000 mmol, 76 mg) were stirred at 70 °C under argon for three hours. The reaction mixture was cooled to 50 °C and treated with DDQ (3.000 mmol, 681 mg) and stirred at 50 °C for 15 minutes, at which point the oxidation was done. The reaction mixture was treated with Et3N (16.00 mmol, 2.2 mL) and BF3.OEt2(24.00 mmol, 3.0 mL). The addition of Et3N (16.00 mmol, 2.2 mL) and BF3.OEt2(24.00 mmol, 3.0 mL) was repeated, and the reaction mixture heated at 50 °C for one hour. The reaction mixture was quenched with saturated sodium bicarbonate solution, stirred until bubbling ceased, filtered through a polypropylene frit to retain water, eluting with DCM. The DCM was evaporated to near-dryness, ~40g of flash silica gel was added, along with some hexanes, and the mixture evaporated to dryness in vacuo. The silica gel was packed into a loader and the mixture purified by flash chromatography on silica gel (120g, 95% toluene / hexanes isocratic)). Fractions containing product were evaporated to dryness in vacuo to give an orange solid, 259 mg (22% yield). MS (APCI): calculated for Chemical Formula: C33H43BF2N2O4(M+H) 581; found: 581.1H NMR (400 MHz, TCE) δ 7.52 (t, J = 7.8 Hz, 1H), 7.33 (d, J = 7.8 Hz, 2H), 3.80 (s, 6H), 3.70 (p, J = 6.9 Hz, 2H), 2.99 (p, J = 6.7 Hz, 2H), 1.55 (s, 6H), 1.32 (d, J = 7.0 Hz, 12H), 1.11 (d, J = 6.7 Hz, 12H). Compound RD-10 (dimethyl 10-(2,6-diisopropylphenyl)-3,7-diisopropyl-1,9- dimethyl-5,5-bis(2,2,2-trifluoroacetoxy)-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'- f][1,3,2]diazaborinine-2,8-dicarboxylate): Compound RD-10.3 (0.2222 mmol, 129 mg), TMSOTFA (2.222 mmol, 0.38 mL), and BCl3(1.0M toluene, 0.4444 mmol, 0.44 mL) were stirred in dry DCE (10 mL) at room temperature for 15 minutes. The reaction mixture was quenched with saturated sodium bicarbonate solution, stirred until bubbling ceased, filtered through a polypropylene frit to retain water, eluting with DCM. The DCM was evaporated to near-dryness, ~15g of flash silica gel was added, along with some hexanes, and the mixture evaporated to dryness in vacuo. The silica gel was packed into a loader and the mixture purified by flash chromatography on silica gel (80g, 50% toluene / hexanes (2 CV) → 100% (5 CV), stop at 52.0%, isocratic)). Fractions containing product were evaporated to dryness in vacuo to give an orange solid, 83 mg (49% yield). MS (APCI): calculated for Chemical Formula: C37H43BF6N2O8(M+H) 769; found: 769.1H NMR (400 MHz, TCE) δ 7.52 (t, J = 7.8 Hz, 1H), 7.33 (d, J = 7.8 Hz, 2H), 3.80 (s, 6H), 3.70 (p, J = 6.9 Hz, 2H), 2.99 (p, J = 6.7 Hz, 2H), 1.55 (s, 6H), 1.32 (d, J = 7.0 Hz, 12H), 1.11 (d, J = 6.7 Hz, 12H). Preparation of green pixel film Solution preparation Solution 1.1 is prepared by dissolving 15% PETG polymer solution in cyclopentanone. Solution 1.2 is prepared by adding 30% TiO2(200nm diameter) to Solution 1.1 with stirring plus sonicating to obtain a uniform dispersion solution.100mM blue absorber BAC2-3 and second photoluminescent dye (GN-9 -shown below) were added to Solution 1.2, with further stirring and sonicating of the solution. The solution was cast on a PET film substrate using an applicator with a 2 mil gap. The pixel film was baked on 60 °C for 15 minutes, followed by 150 °C for 15 minutes. Preparation of red pixel film Solution preparation Solution 1.1 is prepared by dissolving 15% PETG polymer solution in cyclopentanone. Solution 1.2 is prepared by adding 30% TiO2(200 nm diameter) to Solution 1.1 with stirring plus sonicating to obtain uniform dispersion solution. In 2 ml of solution 1.2, 39 mg of blue absorber BAC2-1 and 3.7 mg of second photoluminescent dye (red emitter) were added. The solution was then further stirred and sonicated under room temperature for about 1 hour. The solution was then casted on a 75 mm PET substrate using an applicator with a 2 mil gap. The coated film was then baked at 60 °C for 15 mins, followed by baking at 150 °C for 15 mins. Preparation of red pixel film with addition green emitter Solution preparation Solution 1.1 was prepared by dissolving 15% PETG polymer solution in cyclopentanone. Solution 1.2 was prepared by adding 30% TiO2(200 nm diameter) to Solution 1.1 with stirring plus sonicating to obtain a uniform dispersion solution. In 2 ml of solution 1.2, 39 mg of blue absorber BAC2-1, 2.3 mg of FRET green emitter and 3.7 mg of non-FRET red emitter were added. The solution was then further stirred and sonicated under room temperature for about 1 hour. The solution was then casted on a 75 mm PET substrate using an applicator with a 2 mil gap. The coated film was then baked at 60 °C for 15 mins, followed by baking at 150 °C for 15 mins. T90 Stability Evaluation T90 is defined as time (h) for emission light intensity to drop to 90% of its original at time=0. Emission light intensity (mW / nm) is measured by MCPD. MCPD stands for multi- channel photon detection (MCPD-9800, Otsuka Electronics). To measure the emission light intensity, a blue LED backlight unit was placed at the bottom, a pixel film was placed between the blue backlight and an opening of a detector integrating sphere. Emitted light was collected in the integrating sphere and detected by MCPD. Optical Density (O.D.) Evaluation Definition of optical density here is the negative of the logarithm (base 10) of the transmission between 400-530 nm. Transmission is the ratio of light intensity (mW / cm2 / nm) at 400-530nm after and before placing pixel film on the light source. Film QY and EQE evaluation Quantum yield of film is determined using a Hamamatsu C11347 Absolute PL quantum yield spectrometer (Hamamatsu Inc., Campbell CA, USA). Film EQE is defined as the equation below:

[0062] Photon number is calculated from emission intensity measured by MCPD. Photostability Study of sharp emitter chromophores

[0063] Table 1

[0064] In Table 1, Examples 1-5 are prepared same way as described in film preparation procedure of Comparison examplel except that the blue absorber was changed according to Table 1.

[0065] Compared to comparison example 1, example 2-5 uses blue absorber in this embodies has higher EQE as well as better photostability (T90).

[0066] Table 2

[0067] Examples 6, 7 and comparison example 2 are made the same way as comparison examplel except green emitter is changed to GN-10, GN-11 and GN-9 respectively.

[0068] GN-10, GN-11 and GN-9 are BODIPY type green emission photoluminescent dyes not covalently bonding with a blue absorber and covalently bonding with one or two blue absorbers respectively. The total amount of blue absorber either independently physically mixed in the film or bonded with BODIPY are fixed to be 100 mM. It can be observed from Table 2 that the film using FRET dye (BODIPY covalently bonded with blue absorber) shows higher photostability.

[0069] Table 3

[0070] As shown in Table 3, by adding green emitter in examples 9 and 10, absorption at 465-565 nm increased from 95.6% to 97.4%. Photo stability T90 (300mW / cm2) was not reduced when adding the additional green emitter. The reason for adding the green dye in red pixel film is to reduce emission between 460-560 nm.

[0071] Table 4

[0072] As shown in Table 4, by maintaining the same optical density, the red pixel film with the additional green emitter uses less blue absorber. In some cases, the red pixel film with the additional green emitter improved photostability. For example, in example 9, T90 was improved ~ 50% compared to Comparison Example 3.

[0073] Table 5 As shown in Table 5, the additional green emitter helps to reduce unwanted light between 460 nm to 550 nm. In comparing example 11 to 12, with additional green emitter 10 mM, optical density (O.D.) increased from 2.2 to 2.4, while photostability T90 doesn’t show any decrease.

[0074] 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 must be in a given sequence, either temporally, spatially, in ranking, or in any other manner.

[0075] 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 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.”

[0076] Unless otherwise indicated, all numbers expressing quantities of ingredients, 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. The term “about” may refer to plus or minus 10% of the indicated number.

[0077] 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 the embodiments, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0078] 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.

[0079] 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.

[0080] 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.”

[0081] 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.

[0082] 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.

[0083] 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.

[0084] 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.

[0085] 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 wavelength converting media, comprising: a film media; a blue light absorbing compound; and a green pixel comprising a first photoluminescent dye including a green narrowly emitting moiety; and a red pixel comprising a second photoluminescent dye including a red narrowly emitting moiety; wherein the blue light absorbing compound, the first photoluminescent dye, and the second photoluminescent dye are disposed within the film media.

2. The wavelength converting media of claim 1, wherein a green wavelength light with an emission spectrum having a full width half maximum of less than about 40 nm is emittable by the green narrowly emitting moiety.

3. The wavelength converting media of claim 2, wherein the green narrowly emitting moiety includes a peak emission at about 510-540 nanometers.

4. The wavelength converting media of claim 1, wherein a red wavelength light with an emission spectrum having a full width half maximum of less than about 50 nm is emittable by the red narrowly emitting moiety.

5. The wavelength converting media of claim 4, wherein the red narrowly emitting moiety includes a peak emission at about 600-660 nm.

6. The wavelength converting media of claim 1 , further comprising scattering centers disposed within the film media.

7. The wavelength converting media of claim 1, wherein the film media comprises a transparent substrate or a translucent substrate.

8. The wavelength converting media of claim 1 , wherein the first photoluminescent dye comprises a FRET green dye.

9. The wavelength converting media of claim 8, wherein the FRET green dye includes a blue light absorbing compound.

10. The wavelength converting media of claim 1, wherein the second photoluminescent dye comprises one of a combination of a FRET green dye and a non- FRET red dye and a combination of anon-FRET green dye and a non-FRET red dye.

11. The wavelength converting media of claim 1, wherein the blue light absorbing compound is according to the following general formula:, wherein: R1is one of an aryl, a C1-C5alkyl substituted aryl and a C1-C8alkyl; and each of R2, R3, R4, R5and R6is independently selected from H and an aryl substituted with at least one trihaloalkyl.

12. The wavelength converting media of claim 11, wherein R1is :

13. The wavelength converting media of claim 11, wherein each of R2, R3, R4, R5 and R6is independently one of H,14. The wavelength converting media of claim 11, wherein the blue light absorbing compound is one of the following:

15. The wavelength converting media of claim 1 , wherein the first photoluminescent dye is one of the following:

16. The wavelength converting media of claim 1 , wherein the second photoluminescent dye is one of the following:

17. The wavelength converting media of claim 1 , exhibiting an internal quantum yield of greater than about 80%.

18. The wavelength converting media of claim 1 , exhibiting an external quantum yield of greater than about 40%.

19. The wavelength converting media of claim 1 , comprising a thickness of less than 10 μm.

20. A printed layer including a wavelength converting media according to any one of claims 1-19, wherein blue light is absorbable by the printed layer and the blue light is convertible by the printed layer to green or red light with sharp emission spectral.

21. The printed layer of claim 20, further comprising a transparent substrate, and wherein the wavelength converting media further includes a plurality of scattering centers.

22. The printed layer of claim 20, further comprising a plurality of dots of the wavelength converting media according to any one of claims 1-19, wherein the plural dots are located over predetermined pixel locations of a light emitting device.

23. The printed layer of claim 22, wherein the plurality of dots are sized to cover the predetermined pixel locations of the light emitting device.

24. A light emitting device including a wavelength converting media according to any one of claims 1-18.

25. A backlit device, comprising a blue light source and a wavelength converting media according to any one of claims 1-18.

Images