Wavelength conversion inkjet composition, film containing the same, and display device

Abstract

This specification describes ink compositions and / or films containing the same having improved quantum efficiency and color gamut. The ink composition and / or film comprises an ink medium, a first blue absorbing compound, and a first photoluminescent dye, wherein the first photoluminescent dye comprises a blue absorbing portion, a linker, and a narrow FWHM green emitting portion. The ink composition may further comprise a second photoluminescent dye, wherein the second photoluminescent dye comprises a blue absorbing portion, a linker, and a narrow FWHM red emitting portion.

Description

[Technical Field]

[0001] [Cross-reference of related applications] This application claims the benefits of U.S. Provisional Patent Application No. 63 / 492,947, filed on 29 March 2023. [Background technology]

[0002] Unless otherwise specified in this disclosure, the details described herein are not prior art to the claims of this application, nor will they be deemed to be prior art by being included in this section.

[0003] Photoluminescent materials are substances that emit light after absorbing energy in the form of light or electricity. Depending on the components and light emission mechanism, photoluminescent materials can be classified into inorganic photoluminescent materials (or dyes), organic photoluminescent dyes, nanocrystalline photoluminescent materials, and so on.

[0004] In recent years, various attempts have been made to modify the spectrum of light sources using such photoluminescent materials. Photoluminescent materials absorb light of specific wavelengths from a light source, convert it into light of longer wavelengths in the visible region, and emit light. Depending on the luminescence characteristics of the photoluminescent material, the brightness, color purity, and color gamut of the emitted light can be significantly improved. Inorganic photoluminescent materials can be formed from parent compounds such as sulfides, oxides, or nitrides and activated ions, and can be used in high-quality display devices with excellent physical and chemical stability and high reproducibility of color purity. However, these inorganic photoluminescent materials have drawbacks in that they are very expensive, have low luminescence efficiency, and emission is limited in the near-ultraviolet or blue region above 400 nm.

[0005] Quantum dot technology achieves high levels of quantum efficiency and color gamut. However, cadmium-based quantum dots can be highly toxic and are restricted in many countries due to health safety concerns. Furthermore, some quantum dots have much lower quantum efficiency when converting blue LED light to green or red light. In addition, quantum dots may have low stability when exposed to moisture and oxygen and often require expensive encapsulation processes. The cost of quantum dots can be high because it can be difficult to control size uniformity during manufacturing.

[0006] Fluorescent inks or toners are described (e.g., U.S. Patent No. 5,681,381; U.S. Patent Application Publication No. 2003 / 00841). However, when using light sources from multiple pixelated light sources of different colors, e.g., blue, green, and red, further problems arise due to the different colored light sources. Some toners or inks incorporate fluorescence resonance energy transfer (FRET) technology, but the quantum yield is not always at the desired level.

[0007] Therefore, a new photoluminescent toner or printer ink is needed for use with pixelated light sources. [Overview of the project]

[0008] This disclosure relates to a wavelength conversion film and an emitting display device including the same.

[0009] In some embodiments, the wavelength-converting inkjet ink (medium) may contain at least a first blue absorption compound and a first photoluminescent dye, the first blue absorption compound and the first photoluminescent dye being disposed within the ink medium. In some embodiments, the first photoluminescent dye may include a portion that absorbs blue wavelength light and a portion that emits light over a narrow range. In some embodiments, the portion that emits light over a narrow range may emit green wavelength light having an emission spectrum with a full width at half maximum of less than 40 nm. In some embodiments, the portion that emits light over a narrow range may have an emission peak in the range of about 520 nanometers to about 535 nanometers. In some embodiments, the portion that emits light over a narrow range may emit wavelength light having an emission spectrum with a full width at half maximum of less than 55 nm. In some embodiments, the portion that emits light over a narrow range may have an emission peak in the range of about 610 nm to about 650 nm.

[0010] In some embodiments, the inkjet ink may further include scattering centers. In some embodiments, the scattering centers may be located within the ink medium. In some embodiments, the inkjet ink may include a transparent ink substrate. In some embodiments, the inkjet ink may include at least a first blue absorbing compound and a FRET dye which is a sharp emitter. In some embodiments, the FRET dye which is a sharp emitter may include a second blue absorbing compound.

[0011] In some embodiments, the blue absorbent compound is given by the general formula: [ka] (In the formula, R1 is an arylcarboxyl, C 4~8 Alkyl, or C 4~10 It can be an alkyl compound, and R2, R3, and R4 can be independently H or tetrahalogen-substituted aryl compounds. In some embodiments, R1 is [ka] or [ka] It is possible.

[0012] In some embodiments, R2, R3, or R4 are independently H, [ka] , or [ka] It is possible.

[0013] In some embodiments, the blue absorbent compound is [ka] [ka] [ka] It is possible.

[0014] In some embodiments, the first photoluminescent dye is [ka] [ka] [ka] [ka] [ka] It is possible.

[0015] In some embodiments, the inkjet ink and / or film containing it may have an internal quantum yield of over 80%, an external quantum yield of over 50%, and a color gamut of over 90% of the BT.2020 standard. In some embodiments, the wavelength conversion medium may have a thickness of less than 100 μm.

[0016] In some embodiments, the printed layer may include the inkjet ink described above. In some embodiments, the printed layer may absorb blue light and convert the blue light into green or red light with a sharp emission spectrum, and can be used as a color pixel layer for display applications. In some embodiments, the printed layer may further include a transparent substrate, and the wavelength conversion medium may further include a plurality of scattering centers. In some embodiments, the printed layer may further include a plurality of dots of the inkjet ink described above. In some embodiments, the plurality of dots may be located across predetermined pixel positions of the light-emitting device. In some embodiments, the plurality of dots may be sized to cover predetermined pixel positions of the light-emitting device.

[0017] In some embodiments, the light-emitting device includes a wavelength conversion medium and / or ink composition as described herein. In some embodiments, a backlit device having a blue light source is described, and the backlit device includes a wavelength conversion medium as described herein.

[0018] These embodiments and other embodiments are described in further detail below. [Brief explanation of the drawing]

[0019] [Figure 1] This is a schematic diagram of one embodiment of a display device including a WLC film as described herein. [Figure 2] This is a schematic diagram of one embodiment of a display device including a WLC film as described herein. [Figure 3]This is a schematic diagram of a test configuration including embodiments of the film described herein. [Figure 4] This is a 1931 CIE chromaticity diagram showing the color gamut representation of the WLC films described herein. [Modes for carrying out the invention]

[0020] This disclosure relates to a wavelength conversion medium comprising a photoluminescent compound (or dye) having high quantum efficiency, high color gamut output, and low cost.

[0021] The term "BODIPY" as used herein refers to the formula: [ka] This refers to the chemical part that possesses the characteristic feature.

[0022] The BODIPY portion may consist of a disubstituted boron atom (BX2), typically a dipyromethene complexed with a BF2 or B(CN)2 unit. The IUPAC name for the BODIPY core (i.e., without any substituents and without an aryl group opposite the BX2 group (X=F)) is 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene.

[0023] In some embodiments, R1, R2, R3, R4, R5, and R6 may independently be H, C1-3 alkyl, aryl, ether, ester, and / or phenyl groups. In some embodiments, R7 and R8 may independently be H, a methyl group (-CH3), an aryl group, or Cl.

[0024] The BODIPY portion of this disclosure may have R3 and R4 independently be an aryl group, such as a phenyl group, and R1, R2, R5, and / or R6 independently be H, a substituted aryl group, such as an optionally substituted phenyl group. [ka] [ka] [ka] [ka] ), diphenyl group ( [ka] ), and / or C 2~10 Alkyl ether group ( [ka] ) This could be a BODIPY portion.

[0025] As used herein, the terms "isoquinoline," "isoquinoline derivative," or "xanthenoisoquinoline derivative" refer to the formula: [ka] (In the formula, X is NR, R may be a linking group or an aryl group, and Y may be a hydrogen group, a C1-C3 alkyl group, or an aryl group, such as a benzyl group) refers to the chemical part having these groups.

[0026] As used herein, the terms “naphthalimide” or “naphthalimide derivative” refer to the formula: [ka] (In the formula, R1 is an arylcarboxyl, C4-C8 alkyl, or C4-C 10 This refers to a chemical moiety selected from alkyl groups, where R2, R3, and R4 can independently be H or tetrahalogen-substituted aryl groups.

[0027] In some embodiments, the BODIPY portion may be an independent compound in the ink composition, for example, a first blue light or wavelength absorbing compound. In some embodiments, the BODIPY portion is linked by a linking group to an isoquinoline portion, for example, a first photoluminescent dye, and the first photoluminescent dye may include a blue light or wavelength absorbing portion and a narrow-range emitting portion, for example, a portion that emits green light in a narrow range or a portion that emits red light in a narrow range.

[0028] The term ITU-R Recommendation BT.2020 (more commonly known by the abbreviations Rec.2020 or BT.2020) refers to a color gamut display standard. The RGB primary colors used by Rec.2020 correspond to monochromatic light sources on the CIE1931 spectral locus. The wavelengths of the Rec.2020 primary colors are 630 nm for red, 532 nm for green, and 467 nm for blue. The Rec.2020 color space covers 75.8% of the CIE1931 color space (the region within the defined triangle). Rec.2020 uses the CIE standard light source D65 as the white point and the following color coordinates: Xw=0.3127, Yw=0.3290, XR=0.708, YR=0.292, XG=0.17, YG=0.797, XB=0.131, YB=0.046.

[0029] Some embodiments include a printer ink composition comprising an ink medium, e.g., a solvent or dispersion medium, a first blue light absorbing compound, and an organic photoluminescence compound. In some embodiments, the printing substrate and / or film may comprise the above-described printer ink composition. In some embodiments, the printer ink composition may comprise the first blue light absorbing compound and / or portion. In some embodiments, the first blue light absorbing compound and / or portion is independent of or separate from the linker and / or portion that emits green or red light in a narrow range, for example, is not covalently bonded to it. In some embodiments, the printer ink may comprise a first organic photoluminescence dye that emits green light and has an emission peak with a full width at half maximum of less than 40 nm. In some embodiments, the printer ink composition may comprise an alternative and / or second organic photoluminescence dye that emits red light and has an emission peak with a full width at half maximum of less than 55 nm. In some embodiments, the film may comprise a light scattering center. In some examples, the first blue absorbing portion, the green-emitting organic photoluminescent dye (emitting green light), and / or the second red-emitting organic photoluminescent dye (emitting red light), and / or the scattering center are located within an ink composition comprising an ink suspension medium or dispersion medium and / or a polymer matrix.

[0030] In some embodiments, a printer ink composition or a material containing the same may provide a high quantum yield. In some embodiments, a film provides a wide color gamut of over 90%. A preferred means for determining the percentage color gamut is to measure the area under the generated 1931 CIE color space (e.g., Figure 4). In some embodiments, the ink composition and / or a film containing the same may have a color gamut of 89% to 99.9%, for example, 91%, 92%, 93%, and / or 98%, or a range defined by any of these values. Some embodiments describe an LCD backlight including the film described above.

[0031] In some embodiments, the ink composition and / or the film containing it may include a polymer matrix. In some embodiments, the polymer matrix may have a transparency greater than 75%. In some embodiments, the polymer matrix may include a hydrophilic polymer. In some embodiments, the polymer matrix may include polyvinyl butyral, polyvinyl acetate, polyvinyl alcohol, or polyacrylate. In some embodiments, the polymer matrix may include polyvinyl butyral (PVB). In some embodiments, the polymer matrix may include ethyl cellulose and / or polyester or copolymers containing them. In some embodiments, the polyacrylate may be polyalkyl acrylate. In some embodiments, the polyalkyl acrylate may be polymethyl methacrylate (PMMA).

[0032] The colorants described herein are useful as colorants in inks, such as inkjet inks, such as those with an aqueous or non-aqueous base, and microemulsion inks, and may also be useful as colorants in inks that operate according to the hot-melt principle.

[0033] In some embodiments, the ink composition and / or film containing it may contain a nonpolar solvent, such as a nonpolar organic solvent, and / or a polar solvent. In some embodiments, the ink composition and / or film containing it may be dispersed, dissolved, and / or mixed with the solvent. In some embodiments, the solvent may be used in the manufacture of a material layer. In some embodiments, the solvent may be used for use in a printer cartridge, or for placement on a desired substrate, or for dispersing or solubilizing blue absorption portions, fluorescent portions, etc., in the manufacture of a material layer. In some embodiments, the solvent may be a nonpolar solvent. In some embodiments, examples of nonpolar solvents include, but are not limited to, xylene, cyclohexanone, acetone, toluene, methyl ethyl ketone, or any combination thereof. In some embodiments, the solvent may be a polar solvent. In some embodiments, the polar solvent may include ethanol, dimethylformamide (DMF), or a combination thereof. In some embodiments, the solvent may be a combination of a nonpolar solvent and a polar solvent. A suitable example of a solvent-based inkjet ink is a transparent ink using a very mild solvent containing 2-ethoxyethyl ether (product number SB.UMS.3000, STS inks, Boca Raton, Florida, USA).

[0034] Inkjet inks generally contain one or more of the compounds described herein in total amount of 0.5% to 15% by weight, or more specifically, about 1.5% to 8% by weight (on a dry weight basis). Microemulsion inks are based on organic solvents and water, with or without additional hydrotropic substances (interfacial mediators). Microemulsion inks may contain 0.5% to 15% by weight, or 1.5% to 8% by weight, one or more of the compounds described herein, 5% to 99% by weight of water, and 0.5% to 94.5% by weight of organic solvents and / or hydrotropic compounds, but other variations of these amounts and ranges are also possible and intended.

[0035] Solvent-based inkjet inks may contain 0.5% to 15% by weight of one or more compounds according to the present disclosure and 85% to 99.5% by weight of organic solvents and / or hydrotropic compounds, but other variations in these amounts and ranges are also possible and intended.

[0036] Hot melt inks are primarily based on waxes, fatty acids, fatty alcohols, or sulfonamides that are solid at room temperature, liquefy upon heating, and have a melting range between approximately 60°C and approximately 140°C. Hot melt inkjet inks may essentially consist, for example, of 20% to 90% by weight of wax and 1% to 10% by weight of one or more of the compounds of this disclosure. Hot melt inkjet inks may further contain 0% to 20% by weight of additional polymers (as "pigment solvents"), 0% to 5% by weight of dispersants, 0% to 20% by weight of viscosity modifiers, 0% to 20% by weight of plasticizers, 0% to 10% by weight of tack-imparting agents, 0% to 10% by weight of clarity stabilizers (e.g., to prevent crystallization of wax), and 0% to 2% by weight of antioxidants. Typical additives and auxiliaries are described, for example, in U.S. Patent No. 5,560,760.

[0037] In some embodiments, the photoluminescent compound (and / or a photoluminescent wavelength conversion film containing the photoluminescent compound) has a narrow absorption or emission band, resulting in the emission of a small amount of visible wavelength light. The absorption or emission band can be characterized by its full width at half maximum (FWHM). In this disclosure, FWHM is defined in nanometers as the width of the absorption or emission spectrum at half the peak wavelength of the absorption or emission. In some embodiments, the photoluminescent compound has an absorption band having an FWHM value of 50 nm or less, 40 nm or less, 35 nm or less, 30 nm or less, or 25 nm or less when dispersed in a substantially transparent polymer matrix. In some embodiments, the photoluminescent compound has an emission band having an FWHM value of 50 nm or less, 40 nm or less, 35 nm or less, or 30 nm or less when dispersed in a substantially transparent polymer matrix.

[0038] In some embodiments, the first blue-absorbing compound may contain a naphthalimide group. In some embodiments, the first blue-absorbing compound may contain an isoquinoline alkyl derivative. In some embodiments, the first blue-absorbing compound may be a derivative of a photoluminescent dye described in concurrently pending U.S. Provisional Application No. 63 / 152,309 (a discussion of photoluminescent dyes, which is incorporated herein by reference), U.S. Provisional Application No. 63 / 278,904 (agency reference number N3253.10133US02, which is incorporated herein by reference), and U.S. Provisional Application No. 63 / 379,633 (agency reference number N3253.10153US02, which is incorporated herein by reference).

[0039] In some embodiments, the first blue-absorbing compound is [ka] [ka] [ka] You can choose from these options.

[0040] In some embodiments, the blue-absorbing compound may be similar to or identical to the blue-absorbing portion of the green-emitting compound and / or red-emitting compound described herein. In some embodiments, the blue-absorbing compound may be a derivative of a different blue-absorbing portion of the green-emitting compound and / or red-emitting compound described herein.

[0041] In some embodiments, the printer ink may contain a first organic photoluminescent dye, which may contain a BODIPY group, a linking group, and an isoquinoline group. In some embodiments, the isoquinoline group may be an isoquinoline derivative group. In some embodiments, the isoquinoline group may be a xanthenoisoquinoline derivative group. In some embodiments, the BODIPY group is covalently bonded to the linking group. In other embodiments, the linking group is covalently bonded to the isoquinoline group. In other embodiments, the linking group is covalently bonded to the isoquinoline derivative group. In other embodiments, the linking group is covalently bonded to the xanthenoisoquinoline derivative group.

[0042] In some embodiments, the printer ink composition and / or the film containing the same may contain a first organic photoluminescent compound (or dye). In some embodiments, the first organic photoluminescent dye (and / or the photoluminescent wavelength conversion film containing the first organic photoluminescent dye) may have an emission peak in the range of about 510 nm to about 540 nm. In some embodiments, the emission peak may be at approximately 500 nm to 515 nm, approximately 515 nm to 520 nm, approximately 520 nm to 525 nm, approximately 525 nm to 530 nm, approximately 530 nm to 535 nm, approximately 535 nm to 540 nm, approximately 540 nm to 545 nm, approximately 545 nm to 550 nm, approximately 550 nm to 555 nm, approximately 555 nm to 560 nm, or approximately 510 nm, approximately 520 nm, approximately 530 nm, approximately 540 nm, or any wavelength (green light emission) defined by any of these values. In some embodiments, the emission spectrum of the first organic photoluminescent dye and / or photoluminescent wavelength conversion film may have a full width at half maximum (FWHM) of less than approximately 50 nm, less than approximately 45 nm, less than approximately 40 nm, less than approximately 35 nm, less than approximately 30 nm, less than approximately 25 nm, or less than approximately 20 nm.

[0043] In some embodiments, the first organic photoluminescent dye may be selected from the photoluminescent dyes described in concurrently pending U.S. Provisional Application No. 63 / 152,309 (which, with respect to the discussion of photoluminescent dyes, is incorporated herein by reference) and U.S. Provisional Application No. 63 / 278,904 (which, by reference, is incorporated herein by reference, agent reference number N3253.10133US02).

[0044] In some embodiments, the first organic photoluminescent dye is GN-1 and / or GN-2: [ka] [ka] , or a combination thereof may be selected.

[0045] In some embodiments, the wavelength-converting ink or a film containing the same may contain a second organic photoluminescent dye. In some embodiments, the wavelength-converting film may contain both the first organic photoluminescent dye and the second organic photoluminescent dye. In some embodiments, the second organic photoluminescent dye (and / or a photoluminescent wavelength-converting film containing the second organic photoluminescent dye) may have an absorption peak (blue light absorption) in the range of 400 nm to 470 nm. In some embodiments, the second organic photoluminescent dye (and / or a photoluminescent wavelength-converting film containing the second organic photoluminescent dye) may have an emission peak in the range of about 600 nm to about 660 nm. In some embodiments, the emission peak may be at approximately 600nm-605nm, approximately 605nm-610nm, approximately 610nm-615nm, approximately 615nm-620nm, approximately 620nm-625nm, approximately 625nm-630nm, approximately 630nm-635nm, approximately 635nm-640nm, approximately 640nm-645nm, approximately 645nm-650nm, approximately 650nm-655nm, approximately 655nm-660nm, or any wavelength (red light emission) within the range defined by approximately 600nm, approximately 610nm, approximately 620nm, approximately 630nm, approximately 640nm, approximately 650nm, approximately 660nm, or any of these values. In some embodiments, the emission spectrum of the second organic photoluminescent dye and / or photoluminescent wavelength conversion film may have a full width at 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.

[0046] In some embodiments, the second organic photoluminescent dye may be selected from the photoluminescent dyes described in concurrently pending U.S. Provisional Application No. 63 / 248,863 (on the subject of photoluminescent dyes, which is incorporated herein by reference), U.S. Provisional Application No. 63 / 278,944 (agency reference number N3252.10147US02, which is incorporated herein by reference), and the PCT patent publication International Publication No. 2020 / 210761 (which is incorporated herein by reference). In some embodiments, the second organic photoluminescent dye may be RD-1, RD-2, and / or RD-3: [ka] [ka] [ka] Alternatively, any combination thereof may be selected.

[0047] In some embodiments, the first photoluminescent compound absorbs light from within the UV / blue absorption spectrum and emits light having an emission spectrum that overlaps with the absorption spectrum of the second dye, thereby enabling FRET migration and thus enhancing the perceived emitted green light. In other embodiments, the second photoluminescent compound absorbs light from within the green and / or blue absorption spectrum and emits light within the red emission spectrum, thereby enhancing the perceived emitted red light.

[0048] In some embodiments, the first and second photoluminescent dyes can absorb about 60% to 70% of the light emitted from a light source in the blue spectrum. In some embodiments, the resulting white light includes 30% to 50% blue light, 20% to 30% red light emitted from the wavelength-converting film, and 20% to 30% green light emitted from the wavelength-converting film. The thickness of the film can be adjusted to control the proportion of blue light absorbed by the wavelength-converting film and the proportion of blue light that passes through the wavelength-converting film and constitutes the resulting light. The amount of blue light that can be absorbed can be adjusted depending on the number of printing cycles / layers. For example, in some embodiments, the film may be thick enough to absorb more than 75%, more than 80%, more than 90%, and / or more than 95% of the blue light. In some embodiments, the photoluminescent wavelength-converting film may have any preferred thickness, e.g., less than about 500 μm, less than about 200 μm, or less than about 100 μm. In some embodiments, the photoluminescent wavelength conversion film may have a thickness of approximately 1 μm to 20 μm, approximately 20 μm to 30 μm, approximately 30 μm to 40 μm, approximately 40 μm to 50 μm, approximately 50 μm to 80 μm, approximately 80 μm to 120 μm, approximately 120 μm to 200 μm, approximately 200 μm to 300 μm, approximately 300 μm to 500 μm, or any thickness within a range defined by any of these ranges. In some embodiments, the final thickness of the film at a particular selected location, and therefore the amount of blue light absorbed, can be increased by applying an ink and / or a layer containing it multiple times at the same location.

[0049] In some embodiments, the solubility of the first and second photoluminescent dyes can be optimized by adjusting the length of the linking groups. In some embodiments, the solubility of the first and second photoluminescent dyes may be greater than 0.15%. In some embodiments, the solubility of the first and second photoluminescent dyes may be about 0.03% to 0.8%, about 0.8% to 2%, or about 2% to 3%, or any solubility within a range defined by any of these ranges.

[0050] The color characteristics of the photoluminescent wavelength conversion film can be adjusted by adjusting the ratio of the amount of the first blue absorber compound or portion (e.g., an independent blue portion) to the amount of the second blue absorber portion (e.g., the blue absorber portion of the blue absorber portion-linker-emitter portion). For example, the weight ratio of the first blue absorbent portion to the second blue absorbent portion can be approximately 0.01 to 100 (where 1 mg of the first blue absorbent portion and 100 mg of the second blue absorbent portion are in a ratio of 0.01), approximately 0.01 to 0.2, approximately 0.2 to 0.4, approximately 0.4 to 0.6, approximately 0.6 to 0.8, approximately 0.8 to 1, approximately 1 to 2, approximately 2 to 3, approximately 3 to 4, approximately 4 to 5, approximately 5 to 6, approximately 6 to 7, approximately 7 to 8, approximately 8 to 9, approximately 9 to 10, approximately 10 to 20, approximately 20 to 40, approximately 40 to 70, approximately 70 to 100, or approximately 0.43, approximately 0.91, approximately 1.8, approximately 3.0, or any weight ratio defined by any of these values.

[0051] In some embodiments, the film may further include a transparent substrate. In some embodiments where the film includes a transparent substrate, the wavelength conversion medium may include scattering centers located within the ink medium. In some embodiments, the film may include scattering centers located within a polymer matrix. In some embodiments, the scattering centers may be solid particles comprising a scattering material having a refractive index (RI) different from that of the polymer matrix material. The scattering material may be a material whose refractive index is different from that of the polymer matrix's RI. The scattering material may be useful in increasing the external quantum yield, for example, by reducing total internal reflection.

[0052] [Table 1]

[0053] In some embodiments, the RI difference 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, and at most about 1 or about 2, but other variations are possible and intended.

[0054] In some embodiments, the scattering material may be silicone beads. In some embodiments, the scattering centers may include air pores defined within the polymer matrix. In some embodiments, the scattering centers may have an average diameter of 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 within the range defined by any of these values. In some embodiments, the scattering centers may be substantially uniformly dispersed within the polymer matrix. In some embodiments, the uppermost portion of the film, for example, distal to the blue light source, may have more than 50% scattering centers. In some embodiments, the scattering centers can be uniformly distributed throughout the polymer matrix.

[0055] In some embodiments, the ink composition may not contain the scattering centers described above. In some embodiments where the ink composition does not contain scattering centers, a polymer containing scattering centers can be coated onto a non-glossy substrate.

[0056] In some embodiments, the polymer matrix / ink may have a viscosity of about 0.1 cP to about 75 cP. In some embodiments, the polymer matrix / ink may have viscosities of about 0.1 cP to 1 cP, about 1 cP to 5 cP, about 5 cP to 10 cP, about 10 cP to 15 cP, about 15 cP to 20 cP, about 20 cP to 25 cP, about 25 cP to 30 cP, about 30 cP to 35 cP, about 35 cP to 40 cP, about 40 cP to 45 cP, about 45 cP to 50 cP, about 50 cP to 55 cP, and about 55 cP. It may have viscosities of approximately cP to 60 cP, approximately 60 cP to 65 cP, approximately 65 cP to 70 cP, approximately 70 cP to 75 cP, approximately 0.01 cP, approximately 0.1 cP, approximately 0.5 cP, approximately 1.0 cP, approximately 5.0 cP, approximately 7.5 cP, approximately 10.0 cP, approximately 15.0 cP, approximately 25.0 cP, approximately 50.0 cP, approximately 75.0 cP, or any viscosity within the range defined by any of these values.

[0057] In some embodiments, the wavelength conversion medium may have an internal quantum yield (IQE) greater than 0.8 (80%), greater than 0.81 (81%), greater than 0.82 (82%), greater than 0.83 (83%), greater than 0.84 (84%), greater than 0.85 (85%), greater than 0.86 (86%), greater than 0.87 (87%), greater than 0.88 (88%), greater than 0.89 (89%), greater than 0.9 (90%), greater than 0.91 (91%), greater than 0.92 (92%), greater than 0.93 (93%), greater than 0.94 (94%), or greater than 0.95 (95%), and may be up to approximately 1 (100%) at the maximum value of red or green emission. In some embodiments, the wavelength conversion medium may have an external quantum yield (EQE) of more than 50%, or more than 55%, or more than 60%, or more than 65%, or more than 70%, or more than 75%, or more than 80%, or more than 85%, or more than 90%, or more than 95%, and may be up to about 100% at the maximum value of red or green emission.

[0058] In some embodiments, the ink compositions described herein can be constructed and / or arranged on a printed layer using a printer having a predetermined resolution and / or predetermined pixel positions. In some embodiments, the printed particles may have a size substantially the same as the size of a single pixel or dot printed using a predetermined resolution. In some embodiments, the printed particles may have a position substantially the same as the position of a single pixel of a display device, and may have a single pixel or dot printed at a predetermined pixel position.

[0059] In some embodiments, the printed layer may further include a substrate. In some embodiments, the substrate may include a non-glossy substrate. In some embodiments, the substrate may include a transparent substrate. In embodiments where the substrate includes a transparent substrate, the ink composition may further include scattering centers.

[0060] For example, consider a printer with a resolution of 300 dots per inch (DPI). The "dot size" with such a printer is approximately 84.67 microns. The size of encapsulated covert particles containing covert pigment can be approached to this maximum size of approximately 84.67 microns without interfering with the printing of the display or causing an excessively uneven distribution of the encapsulated covert particles. This is especially true when the printed area is relatively small (e.g., smaller than 1 inch x 2 inches). For a 600 DPI printer, the size of encapsulated particles containing the blue absorption portion and / or the first fluorescence emission portion and / or the second fluorescence emission portion can similarly approach a "dot size" of 42.66 microns; for a 1200 DPI printer, the size of encapsulated particles containing covert pigment can similarly approach a "dot size" of 21.17 microns; and for 4000 DPI, it is 6.35 microns, and so on.

[0061] In some embodiments, the display device can be represented by a device such as device 10. As shown in Figure 1, the display device includes a light source, for example, light source 12. The display device also includes a wavelength conversion (WLC) film, for example, film 16. In some embodiments, the WLC film can be optically connected to the light source to improve the efficiency of transmitting the generated light from the light source to an observer, for example, observer 20.

[0062] In some embodiments, a display device can be schematically represented by Figure 2. As shown in Figure 2, a display device such as device 10 includes a light source, for example, light source 12. In some embodiments, the light source may include a plurality of individual light sources, for example, pixels of the same or different colors, for example, red, green and / or blue (cyan). In some embodiments, individual pixels may have predetermined positions within the intervening light source element. In some embodiments, individual pixels of a particular green and / or red color may have predetermined positions within the intervening light source element. In some embodiments, an ink composition or film incorporating the ink composition described herein can be constructed, printed or otherwise repositioned on a substrate using a printer having such predetermined positions and resolutions, and the particle, ink dot size can be substantially the same size and / or position as a single pixel or dot printed or positioned within the film, printed element or substrate using the predetermined resolution and / or position.

[0063] The display device 10 also includes a back reflector, for example, a back reflector 14, a wavelength conversion (WLC) film, for example, a film 16, and a mask, for example, a mask 18, the mask may be a color filter. In some embodiments, the WLC film can be optically connected to a light source to improve the efficiency of transmitting the generated light from the light source to an observer, for example, observer 20. In some embodiments, the WLC film 16 can be optically connected to a light source 12 and / or sandwiched between the light source 12 and the observer 20 and / or the mask 18 to improve the efficiency of transmitting the generated light from the light source 12 to the observer 20.

[0064] In some embodiments, a backlit device having a blue light source is described. In some embodiments, the backlit device includes the above-described wavelength conversion medium or ink composition.

[0065] Some embodiments include methods for manufacturing LED light sources. In some embodiments, the method may include the production of an undried wavelength-shifted polymer layer with an organic solvent and a photoluminescent dye described herein. In some embodiments, the method may include mixing the polymer and / or monomer with an organic solvent. In some embodiments, the polymer and / or monomer precursor may be dispersed, dissolved, and / or mixed with the solvent. In some embodiments, the solvent can be used to produce the material layer. In some embodiments, the solvent may be a nonpolar solvent. In some embodiments, nonpolar solvents may include, but are not limited to, xylene, cyclohexanone, acetone, toluene, methyl ethyl ketone, or any combination thereof. In some embodiments, the solvent may be a polar solvent. In some embodiments, the polar solvent may include ethanol, dimethylformamide (DMF), or a combination thereof. In some embodiments, the solvent may be a combination of a nonpolar solvent and a polar solvent.

[0066] In some embodiments, the method may involve immersing an undried polymer photocatalytic WLC layer in an aqueous solution. In some embodiments, the aqueous solution may contain water. In some embodiments, the aqueous solution may contain at least 90% water. In some embodiments, the water may be deionized water. In some embodiments, the undried polymer photocatalytic WLC layer can be immersed in the aqueous solution for 5 minutes to about 1 hour.

[0067] In some embodiments, the method may include removing the undried polymer photocatalytic WLC layer from an aqueous solution. In some embodiments, the method may include drying the undried polymer photocatalytic WLC layer. It is believed that producing the polymer photocatalytic WLC layer in this manner results in a plurality of air pores defined on the luminescent surface or distal surface of the polymer photocatalytic WLC layer. In some embodiments, the air pores are substantially entirely located within about 1 to 5 microns from the luminescent surface of the polymer photocatalytic WLC layer.

[0068] In some embodiments, the polymer material includes aqueous solutions of polymers in amounts of about 2% to about 50% by weight, about 2% to 5% by weight, about 5% to 10% by weight, about 10% to 15% by weight, about 15% to 20% by weight, about 20% to 25% by weight, about 25% to 30% by weight, about 30% to 35% by weight, about 35% to 40% by weight, about 40% to 45% by weight, about 45% to 50% by weight, about 2.5% to 30% by weight, about 5% to 15% by weight, about 15% to 25% by weight, about 25% to 35% by weight, or about 30% by weight, or substantially all values ​​within the range defined by any of these values.

[0069] The embodiments and methods will be described in more detail below.

[0070] Embodiment Embodiment 1. A wavelength conversion medium, Ink media and, At least one blue-absorbing compound, A first photoluminescent dye comprising a portion that absorbs blue wavelength light and a portion that emits light over a narrow range, A wavelength conversion medium comprising a blue absorption compound and a first photoluminescent dye, wherein these are arranged within the ink medium.

[0071] Embodiment 2. The wavelength conversion medium of Embodiment 1, wherein the portion emitting within a narrow range is capable of emitting green wavelength light having an emission spectrum with a full width at half maximum of less than 40 nm.

[0072] Embodiment 3. The wavelength conversion medium of Embodiment 2, wherein the portion that emits light over a narrow range has an emission peak in the range of 520 nanometers to 535 nanometers.

[0073] Embodiment 4. The wavelength conversion medium of Embodiment 1, wherein the portion emitting within a narrow range is capable of emitting red wavelength light having an emission spectrum with a full width at half maximum of less than 55 nm.

[0074] Embodiment 5. The wavelength conversion medium of Embodiment 4, wherein the portion that emits light over a narrow range has an emission peak in the range of 610 nm to 650 nm.

[0075] Embodiment 6. The wavelength conversion medium of Embodiment 1, further comprising a scattering center, wherein the scattering center is located within the ink medium.

[0076] Embodiment 7. The wavelength conversion medium of Embodiment 1, wherein the ink medium includes a transparent ink substrate.

[0077] Embodiment 8. The wavelength conversion medium of Embodiment 1, further comprising a FRET dye which is a sharp emitter.

[0078] Embodiment 9. The wavelength conversion medium of Embodiment 8, wherein the FRET dye, which is a sharp emitter, contains a second blue-absorbing compound.

[0079] Embodiment 10. The blue absorption compound has the following general formula: [ka] (In the formula, R1 is an arylcarboxyl, C4-C8 alkyl, or C4-C 10 A wavelength conversion medium of Embodiment 1, which is a compound selected from alkyl groups, wherein R2, R3, and R4 may independently be H or tetrahalogenated aryl groups.

[0080] Embodiment 11.R1 independently, [ka] or [ka] A wavelength conversion medium according to embodiment 10, which may be a possible embodiment.

[0081] Embodiment 12. R2, R3, or R4 independently, H, [ka] or [ka] A wavelength conversion medium according to embodiment 10, which may be a possible embodiment.

[0082] Embodiment 13. The blue absorber compound is [ka] [ka] [ka] A wavelength conversion medium according to embodiment 10, which may be a possible embodiment.

[0083] Embodiment 14. The first photoluminescent dye is [ka] [ka] [ka] [ka] [ka] A wavelength conversion medium according to Embodiment 1, which may be a possible embodiment.

[0084] Embodiment 15. A wavelength conversion medium according to Embodiments 1 to 14, wherein the wavelength conversion medium has an internal quantum yield of more than 80%.

[0085] Embodiment 16. A wavelength conversion medium according to Embodiments 1 to 14, wherein the wavelength conversion medium has an external quantum yield of more than 50%.

[0086] Embodiment 17. A wavelength conversion medium according to Embodiments 1 to 14, wherein the wavelength conversion medium has a color gamut exceeding 90% of the BT.2020 standard.

[0087] Embodiment 18. A wavelength conversion medium according to Embodiments 1 to 17, wherein the wavelength conversion medium has a thickness of less than 100 μm.

[0088] Embodiment 19. A printing layer comprising a wavelength conversion medium of Embodiments 1 to 18, wherein the printing layer absorbs blue light and converts the blue light into green or red light with a sharp emission spectrum, and can be used as a color pixel layer for display applications.

[0089] Embodiment 20. The printed layer of Embodiment 19, further comprising a transparent substrate, wherein the wavelength conversion medium further comprises a plurality of scattering centers.

[0090] Embodiment 21. The print layer of Embodiment 19, further comprising a plurality of dots of the wavelength conversion medium of Embodiments 1 to 18, wherein the plurality of dots are located across predetermined pixel positions of a light-emitting device.

[0091] Embodiment 22. The printed layer of Embodiment 21, wherein a plurality of dots are sized to cover predetermined pixel positions of a light-emitting device.

[0092] Embodiment 23. A light-emitting device comprising the wavelength conversion medium of Embodiments 1 to 18.

[0093] Embodiment 24. A backlit device having a blue light source, comprising the wavelength conversion medium of Embodiments 1 to 18. [Examples]

[0094] Embodiments of wavelength-converting inkjet inks described herein have been found to have improved performance compared to other forms of color-converting films. These advantages are further demonstrated by the following examples, which are intended to be illustrative of the disclosure and not to limit its scope or underlying principles.

[0095] Synthesis of blue light absorber compounds BAC-1 synthesis procedure [ka]

[0096] Compound BAC-1.2: Step 1: A mixture of BAC-1.1 (0.735 g, 2.0 mmol, 1.0 equivalent) and 4-aminophenylbutanoic acid (0.788 g, 4.4 mmol, 2.2 equivalents) was placed in a 20 ml vial fitted with a septum cap and sealed with the septum cap. 5 ml of anhydrous DMF was added, followed by 30 mg of DMAP. The resulting mixture was stirred at 165°C for 2 hours. After cooling to room temperature, the reaction product was washed with 1 N HCl (2 mL) and water (10 ml x 2) at room temperature for 15 minutes, and then filtered. The crude product was used in the next step without further purification.

[0097] Compound BAC-1.3: Step 2: At room temperature, the crude product from the above step was mixed with DMF (5 ml), H2O (0.5 ml), 4-fluoromethylbenzeneboronic acid (0.759 g, 4.0 mmol, 2 equivalents), K2CO3 (0.553 g, 4.0 mmol, 2 equivalents), and Pd(dppf)Cl2·DCM (32.66 mg, 0.04 mmol, 0.02 equivalents). Three vacuum-argon packing cycles were performed, and the mixture was heated with stirring at 80°C for 45 minutes until the mixture became viscous. 5 ml of DMF was added, and stirring was continued at 80°C for a further 15 minutes. The reaction mixture was cooled to room temperature, concentrated using a rotary evaporator, water was added to the residual mixture, and it was held at room temperature for 1 hour. The precipitate was filtered to obtain a greenish-yellow crude solid, which was washed with water to obtain 0.731 g of the desired product. 61% yield. MS(APCI): Chemical formula C 35 H 22 Calculated value (M-) for F3NO5: 593; Measured value: 593. 1 H NMR(400MHz,DMSO-d6) δ12.11(s,1H), 8.65(d,J=2.2Hz,1H), 8.47(s,1H), 8.43~8.31(m,1H), 8.08(d,J=8.1Hz,2H) , 7.98(dd,J=8.6,2.0Hz,1H), 7.85(d,J=8.2Hz,2H), 7.69(d,J=7.9Hz,1H), 7.57(d,J=8.6Hz, 1H), 7.43(d,J=8.3Hz,1H), 7.33(d,J=8.1Hz,2H), 7.24(d,J=8.0Hz,2H), 4.05(t,J=6.6Hz,1H ), 2.70(dd,J=15.8,8.1Hz,2H), 2.30(t,J=7.4Hz,2H), 1.98~1.74(m,2H), 1.47~1.28(m,1H).

[0098] Compound BAC-1: A mixture of BAC-1.3 (1 g, 1.68 mmol, 1 equivalent) and DMAP-pTSA (987.84 mg, 3.36 mmol, 2 equivalents) was added to EDC·HCl (966 mg, 5.04 mmol, 3 equivalents) in anhydrous DCM (45 mL), and then n-BuOH (2 mL) was added. The resulting mixture was stirred at room temperature for 45 minutes under an argon atmosphere. The mixture was concentrated to dryness. The residue was dissolved in DCM (5 mL) and loaded onto a 40 g SiO₂ column. It was eluted with Hex-DCM (7 / 3), and then gradually with only DCM. Pure fractions were collected, concentrated, and dried in a vacuum oven to obtain 375 mg of a yellow solid. 90% yield. MS (APCI): Calculated for C 39 H 30 F₃NO₅ (M⁻) = 649; Found: 649. 1 ¹H NMR (400 MHz) δ 8.55 (d, J = 7.8 Hz, 1H), 8.51 (d, J = 8.3 Hz, 1H), 8.16 (d, J = 2.2 Hz, 1H), 7.98 (d, J = 8.0 Hz, 1H), 7.78 - 7.62 (m, 5H), 7.43 (d, J = 8.6 Hz, 1H), 7.36 - 7.30 (m, 2H), 7.29 (d, J = 8.3 Hz, 1H), 7.20 - 7.10 (m, 2H), 4.02 (t, J = 6.7 Hz, 2H), 2.69 (t, J = 7.7 Hz, 2H), 2.34 (t, J = 7.4 Hz, 2H), 1.95 (p, J = 7.5 Hz, 2H), 1.60 - 1.53 (m, 2H), 1.38 - 1.26 (m, 2H), 0.87 (t, J = 7.3 Hz, 3H).

[0099] Synthesis procedure of BAC-2 Compound BAC-2:

Chemical Structure

[0100] BAC-2.2(5,11-dibromo-1H,3H-isochromeno[6,5,4-mna]xanthene-1,3-dione): A stirring bar was placed in a 2 L 2N round-bottom flask, and a long-finned condenser was attached. 1H,3H-isochromeno[6,5,4-mna]xanthene-1,3-dione) (synthesized in an external laboratory) (34.688 mmol, 10.00 g) was added to the flask, followed by the addition of ortho-dichlorobenzene (1000 mL). The reaction mixture was stirred at room temperature, and Br2 (416.26 mmol, 21.3 mL) was added. The second opening was stoppered, and the reaction mixture was heated to 75°C over the weekend using an aluminum heat block, with the air exposed. The reaction mixture was cooled to room temperature, and the solid was filtered off. The filtrate was diluted with hexane (approximately 20% by volume), and the second precipitate was filtered off. Both of these precipitates were dried at 100°C in a vacuum. An orange-colored solid was obtained, totaling 10.866 g (69.9% yield). LC-MS and NMR were identical. MS(APCI): Chemical formula C 18 Calculated value for H6Br2O4: (M+H) = 445; Measured value: 445. 1 H NMR(400MHz,TCE) δ9.47(dd,J=8.4,1.5Hz,1H), 8.76(d,J=14.2Hz,2H), 7.72~7.63(m,1H), 7.56(dd,J=8.3,1.4Hz,1H), 7.46(ddd,J=8.5,6.7,1.9Hz,1H).

[0101] BAC-2.3(5,11-dibromo-2-(2-ethylhexyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione):BAC-2.2 (7.278 mmol, 3.261 g), 2-ethylhexane-1-amine (14.556 mmol, 2.4 mL), and DMAP (2.183 mmol, 267 mg) were combined in 100 mL of 2N 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 to pH 1 and then diluted with water (approximately 100 mL). The resulting precipitate was filtered and washed with water. The compound was dried by suction for several hours and then divided into two equal parts, which were used in the next reaction without further purification. A 100% yield was assumed for the next step. MS(APCI):Chemical formula:C 26 H 23 Calculated value (M+H) for Br2NO3: 556; Measured value: 556.

[0102] BAC-2(2-(2-ethylhexyl)-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione):BAC-2.3 (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 250 mL of 2N RBF with 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 under vacuum. The residue was placed in DCM, evaporated under vacuum on approximately 20 g of flash silica gel, and placed in a loader. Purification was performed by flash chromatography on silica gel (220 g, equilibrated with 50% hexane / DCM, eluted with 50% (2 CV) → 100% DCM (20 CV)). The fraction containing the product was evaporated to dryness under vacuum. A yellow solid, 2.070 g (82% yield from BAC-2.2), was obtained. MS(APCI): Chemical formula: C 40 H 31Calculated value for F6NO3 (M+H) = 688; measured value: 688. 1 H NMR(400MHz,TCE) δ8.70(s,1H), 8.45(s,1H), 7.91(d,J=8.2Hz,2H), 7.83(dd,J=8.3,6.6Hz,4H) , 7.65(d,J=8.0Hz,2H), 7.39(ddd,J=8.5,7.1,1.5Hz,1H), 7.28(dd,J=8.3,1. 3Hz,1H), 7.09(dd,J=8.4,1.5Hz,1H), 6.93(ddd,J=8.4,7.1,1.3Hz,1H), 4.22 ~3.99(m,2H), 1.95(hept,J=3.7Hz,1H), 1.49~1.22(m,8H), 1.00~0.83(m,6H).

[0103] BAC-3 synthesis procedure [ka] BAC-3(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-2-(2-ethylhexyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione):BAC-3 was synthesized at 80°C using the same method as BAC-2, from BAC-3.1 (3.639 mmol, 2.035 g), (3,5-bis(trifluoromethyl)phenyl)boronic acid (14.556 mmol, 3.754 g), K2CO3 (20.015 mmol, 2.766 g), and Pd(dppf)Cl2 (0.255 mmol, 186 mg) in THF (60 mL), DMF (12 mL), and water (6 mL). Purification of BAC-3 was also carried out using the same method as BAC-2. A yellow solid, 1.913 g (64% yield from BAC-2.2) was obtained. MS (APCI): Chemical formula: C 42 H 29 F 12 Calculated value for NO3 (M+H) = 824; measured value: 824. 1H NMR(400MHz,TCE) δ8.75(s,1H), 8.49(s,1H), 8.28(d,J=1.6Hz,2H), 8.10~7.98(m,4H), 7.46(ddd,J=8.5,5.4,3.3Hz,1H), 7.25(d,J= 8.2Hz,1H), 7.04~6.93(m,2H), 4.24~4.00(m,2H), 1.97(hept,J=6.5Hz,1H), 1.50~1.15(m,8H), 1.00~0.83(m,6H).

[0104] Synthesis of the first photoluminescent dye and the second photoluminescent dye GN-1 synthesis procedure [ka]

[0105] Compound GN-1.1: A mixture of 4-bromo-1,8-naphthalic anhydride (2.77 g, 10 mmol) and 4-bromo-2-nitrophenol (3.27 g, 15 mmol) was degassed under vacuum for 30 minutes, then anhydrous NMP (50 mL) was added, followed by the addition of sodium hydroxide (0.2 g, 5 mmol) and copper powder (0.318 g, 5 mmol). The mixture was sparged with argon for 20 minutes and then heated overnight at 180 °C under an argon atmosphere. After cooling to room temperature, 50 mL of 20% hydrochloric 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 hours, then filtered to collect the precipitate, which was dried under vacuum to obtain 4.6 g of crude product. The crude product was dispersed in 30 mL of acetone and stirred overnight at room temperature to dissolve impurities. After filtering and drying under vacuum, a brownish-yellow solid product was obtained (3.3 g, 80% yield). LCMS(APCI+):C 18 Calculated value (M+H) for H9BrNO6: 413.95; Measured value: 414. 1H NMR(400MHz,TCE-d2) δ8.70(dd,J=8.4,1.2Hz,1H), 8.63(dd,J=7.3,1.2Hz,1H), 8.41(d,J=8.3Hz,1H), 8. 24(d,J=2.4Hz,1H), 7.89~7.79(m,2H), 7.20(d,J=8.7Hz,1H), 6.82(d,J=8.3Hz,1H).

[0106] 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 minutes. After cooling to room temperature, 100 mL of water was added to the mixture while stirring. The resulting mixture was filtered, washed with water, and dried in air and under vacuum to obtain a solid (1.35 g, 82% yield). LCMS(APCI-):C 18 H 10 Calculated value for BrNO4: 382.98; Measured value: 383. 1 H NMR (400MHz, DMSO-d6) δ9.01~8.26 (m, 3H), 7.96 (s, 1H), 6.93 (dd, J=85.2, 36.5Hz, 4H), 5.54 (s, 2H).

[0107] Compound GN-1.3: Compound GN-1.2 (2.65 g, 6.9 mmol) was dispersed in acetic acid (50 mL) / water (10 mL) and cooled to 0°C. While stirring, pre-cooled hydrochloric acid (2.8 mL, 34.5 mmol) was added, followed by the dropwise addition of sodium nitrite solution (3.57 g, 52 mmol) in 15 mL of water at 0°C. After stirring at 0°C for 1 hour, the mixture was transferred to an additional funnel and added dropwise to copper sulfate solution (12 g, 47 mmol, in 140 mL of water) at 130°C over 1 hour. After cooling to room temperature, the precipitate was collected by filtration, washed with water (100 mL x 3), and stirred in 50 mL of acetone at 40°C for 30 minutes. After filtration and drying in air followed by vacuum, a brownish-yellow solid was obtained (1.76 g, 70% yield). LCMS(APCI+):C 18 Calculated value (M+H) for H8BrO4: 366.95; Measured value: 367.1 H NMR(400MHz,d2-TCE) δ8.51(dd,J=12.3,8.1Hz,2H), 8.12(d,J=2.3Hz,1H), 7.86(d,J=7.9Hz,1H) , 7.60(dd,J=8.8,2.3Hz,1H), 7.28(d,J=8.3Hz,1H), 7.23(d,J=8.8Hz,1H).

[0108] [ka]

[0109] Synthesis procedure for compound GN-1.6 [ka]

[0110] Compound FD-2.1: A mixture of ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (1.0 g, 6.0 mmol), 4-hydroxy-2,6-dimethylbenzaldehyde (0.449 g, 3.0 mmol), and p-toluenesulfonic acid (p-TsOH) (50 mg, 0.29 mmol) in 50 mL of dichloroethane (DCE) was degassed and stirred overnight at room temperature. Liquid chromatography-mass spectrometry (LCMS) was performed, yielding m / e + The main peak at =467 indicates that the reaction is complete. 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) (0.817 g, 3.6 mmol) was added to the mixture obtained above, and the whole was stirred at room temperature for 30 minutes. LC-MS analysis was performed, m / e + The main peak at =465 indicates that the reaction is complete. While ice batch cooling, triethylamine (1.7 mL, 12 mmol) and BF3-diethyl ether (2.2 mL, 18 mmol) were added to the mixture obtained above, and the resulting mixture was stirred at 50°C for 1 hour. A further 1 mL of triethylamine and 1 mL of BF3-diethyl ether were added, and the whole was heated for another 1 hour. LCMS analysis showed that all dipyrrolemethine starting materials were m / e +This indicates conversion to the BODIPY product of =513. After cooling to room temperature, the reaction mixture was subjected to silica gel and purified by flash chromatography using hexane / ethyl acetate (0% → 30% ethyl acetate) as the eluent. The desired fraction was collected. After removing the solvent, the desired product was obtained as an orange solid (1.0 g, 65% yield). 1 ¹H NMR (400MHz, chloroform-d): δ 6.68 (s, 2H), 4.29 (q, J=7.1Hz, 4H), 2.84 (s, 6H), 2.05 (s, 6H), 1.34 (t, J=7.1Hz, 6H). LC-MS (APCI+): C 27 H 32 Calculated value (M+H) for BF2N2O5: 513.2; Measured value: 513.

[0111] Synthesis procedure for GN-1.4 - 2-(4-(9-bromo-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinoline-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. The mixture was then heated to 165°C and maintained at this temperature for 3 hours. TLC and LC-MS showed approximately 95% conversion without observable side reactions. The mixture was cooled to 50°C. It was then poured into an acetone solution (40 mL) and pre-cooled in an ice bath. After maintaining the mixture at 0°C for 2 hours, it was stirred overnight at room temperature. The solid was collected by vacuum filtration, washed with acetone (4 mL), and dried in a vacuum oven at 100°C for 3 hours to obtain pure compound GN-1.4 as a yellowish-brown solid (395.0 mg, 73% yield). MS(APCI):C 26 H 14 Calculated value for BrNO5 ([M+H]+) = 500. Measured value: 500. 1H NMR(400MHz,CDCl2CDCl2) δ8.65(d,J=8.0Hz,1H), 8.62(d,J=8.0Hz,1H), 8.21(dd,J=6.4Hz,2.4Hz,1H), 7.99(bs,1H), 7.95(t,J=7.6Hz ,1H), 7.67(dd,J=8.4Hz,2.4Hz,1H), 7.53(d,J=8.0Hz,2H), 7.37(d,J=8.4Hz,1H), 7.32(m,3H), 2.94(s,2H).

[0112] Synthesis procedure for compound GN-1.5 - 2-(4-(1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinoline-2(3H)-yl)phenyl)acetic acid: A stirring bar was attached to a 100 mL vial. Compounds 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) were degassed at room temperature from THF / DMF / H2O (22 ml / 4.4 ml / 2.2 ml). The reaction mixture was heated to 80 °C and maintained at this temperature overnight. The reaction was monitored using TLC. After completion, the reaction was work-treated by adding 0.1 N HCl (150 ml) and SiO (150 ml). The aqueous phase was further extracted with THF (150 ml x 3). The combined organic phase was dried over anhydrous Na2SO4, concentrated under a rotary evaporator (rotavapor), and purified by flash chromatography using DCM in toluene (0% → 40%, containing 0.1% TFA) as the eluent to obtain pure RL-naphthalimide derivative GN-1.5 as a yellow / yellowish-brown solid (363.0 mg, 80% yield). MS(APCI):C 33 H 18 Calculated value for F3NO5 ([M+H]+) = 566. Measured value: 566. 1H NMR(400MHz,DMSO-d6) 8.76(m,1H), 8.56(m,2H), 8.52(dd,J=8.0Hz,J=3.2Hz,1H), 8.15(m,2H), 8.06(m,1H), 7.94(d,J=8.0Hz,2H ), 7.66(dd,J=8.0Hz,J=4.0Hz,1H), 7.53(m,1H), 7.45(d,J=8.0Hz,2H), 7.33(d,J=8.0Hz,2H), 3.72(s,2H).

[0113] 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 of DCM was stirred overnight at room temperature. The reaction mixture was placed on silica gel and purified by flash chromatography using DCM / ethyl acetate (0% → 10% ethyl acetate) as the eluent. 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 obtain an orange solid (45 mg, 72%). LCMS(APCI-):C 60 H 47 Calculated value for BF5N3O9: 1059.33; Measured value: 1059. 1 H NMR (400MHz, methylene chloride-d2) δ8.73(d,J=7.9Hz,1H), 8.66(d,J=8.3Hz,1H), 8.39(d,J=2.2Hz,1H), 8.17(d,J= 8.0Hz,1H), 7.86(dt,J=11.4,8.4Hz,5H), 7.64(d,J=8.3Hz,2H), 7.57(d,J=8.6H) z,1H), 7.43(d,J=8.3Hz,1H), 7.41~7.35(m,2H), 7.09(s,2H), 4.30(q,J=7.1Hz, 4H), 4.05(s,2H), 2.84(s,6H), 2.18(s,6H), 1.77(s,6H), 1.36(t,J=7.1Hz,6H).

[0114] GN-2 synthesis procedure [ka]

[0115] GN-2.1 ((3,5-dibromophenoxy)triethylsilane): A stirring bar was placed in a 500 mL 2N round-bottom flask, and a gas adapter and septum were attached. The flask was placed in a Dewar bowl. The flask was flushed with argon. 3,5-dibromophenol (100.0 mmol, 25.190 g), imidazole (300.0 mmol, 20.430 g), and dry DCM (200 mL) were added to the flask. The mixture was stirred at room temperature to obtain a solution, which was then cooled to 0°C in an ice bath. Chlorotriethylsilane (150.0 mmol, 25.2 mL) was added to the flask by syringe while stirring at 0°C. The reaction mixture was stirred at 0°C for 50 minutes, and then separated with water (200 mL). The layers were separated, and the aqueous layer was extracted with DCM (50 mL). The combined organic layers were dried over MgSO4, filtered, and evaporated to dryness under vacuum. The mixture was diluted with hexane and loaded onto a loader containing 60 g of flash silica gel. Purification was performed by flash chromatography with silica gel (equilibrium and elution with 220 g, 100% hexane). The fraction containing the product was evaporated to dryness under vacuum to obtain 27.811 g (76% yield) of colorless oil. MS(APCI): Chemical formula: C 12 H 18 Calculated value (M+H) for Br2OSi: 365; Measured value: 365. 1 H NMR(400MHz,TCE) δ7.28(t,J=1.7Hz,1H), 6.96(d,J=1.6Hz,2H), 1.10~0.95(m,9H), 0.75(qd,J=7.7,0.9Hz,6H).

[0116] GN-2.2 (2,6-dibromo-4-hydroxybenzaldehyde): A stirring bar was placed in a 250 mL 2N round-bottom flask, and a gas adapter and septum were attached. The flask was placed in a Dewar bowl. The flask was flushed with argon. GN-2.1 (30.00 mmol, 10.985 g) was weighed and azeotropically distilled with toluene. After transferring GN-2.1 to the reaction flask under argon, dry THF (130 mL) was added, and the reaction mixture was stirred at room temperature to obtain a homogeneous solution. The reaction mixture was cooled to -78 °C (dry ice / acetone). Oxygen was removed from the system by vacuum / argon refilling cycles (3 times). The solution of LDA in THF / hexane (1.0 M, 60.00 mmol, 60.0 mL) was added over several minutes with vigorous stirring. The solution was stirred at -78°C for 70 minutes, then anhydrous DMF (150.0 mmol, 11.6 mL) was added by syringe and stirred at -78°C for 60 minutes. The cooled reaction mixture was added to 400 mL of saturated NH4Cl solution with stirring. The solution was extracted with Depositphotos (100 mL) and the layers were separated. The aqueous layer was acidified with an excess of 6N HCl until the pH was approximately 1 to obtain a grayish-white precipitate. The organic layer was extracted with 100 mL of saturated NH4Cl, followed by two extractions with 10% K2CO3 (100 mL). These aqueous extracts were also added to acidified water and the pH was maintained at approximately 1. After filtering the obtained precipitate, it was dried overnight in a vacuum oven at 90°C to obtain a grayish-white / gray precipitate, 6.665 g (79% yield). MS(APCI): Calculated value (M+H) = 281 for chemical formula C7H4Br2O2; measured value: 281. 1 ¹H NMR (400MHz, acetone): δ 10.14 (s, 1H), 7.24 (s, 2H).

[0117] A stirring bar was placed in a 500 mL 2N round-bottom flask containing GN-2.3 (3,3'',5,5''-tetra-tert-butyl-5'-hydroxy-[1,1':3',1''-terphenyl]-2'-carbaldehyde), and a finned condenser / gas adapter and flow control were attached. 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, 5.150 g), 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 was stirred at this temperature overnight. The reaction mixture was evaporated on 60 g of flash silica gel, placed in a loader, and purified by flash chromatography on silica gel (220 g, equilibrated with 0% siRNA / hexane, eluted with 0% (2 CV) → 30% siRNA / hexane (20 CV)). The fraction containing the product was evaporated to dryness under vacuum to obtain a pale yellow solid, 2.256 g (82% yield). MS(APCI): Chemical formula: C 35 H 46 Calculated value for O2 (M+H) = 499; measured value: 499. 1 H NMR (400MHz, TCE) δ9.80(s,1H), 7.42(t,J=1.8Hz,2H), 7.15(d,J=1.8Hz,4H), 6.87(s,2H), 1.35(s,36H).

[0118] 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]isoquinoline-2(3H)-yl)phenyl)acetic acid): 40 mL screw-cap vial, stirring bar, 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]isoquinoline-2(3H)-yl)phenyl)acetic acid (from an external vendor) (5.428 mmol, 4.590 g), D MAP·pTsOH salt (4.523 mmol, 1332 mg) and dry DCM (20 mL) were added. The reaction mixture was stirred at room temperature to obtain a yellow slurry. While stirring at room temperature, DIC (9.047 mmol, 1.41 mL) was added. After stirring the reaction mixture at room temperature for 60 minutes, it was diluted with hexane in a 1:1 ratio and loaded onto approximately 60 g of flash silica gel packed in a loader. The mixture was purified by flash chromatography with silica gel (220 g, equilibrated with 0% siRNA / hexane, eluted with 0% 2CV → 20% siRNA / hexane (22CV)). The fraction containing the product was evaporated to dryness under vacuum to obtain a yellow solid, 5.182 g (86% yield). MS(APCI): Chemical formula: C 77 H 63 F 12 Calculated value for NO6 (M+H) = 1326; measured value: 1326. 1 1H NMR (400MHz, TCE) δ9.89(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=8.6,6.1,2.6Hz,1H), 7.43(t,J=1.8Hz,2H), 7.38(d,J=8.4Hz,2H), 7.31~7.25(m,1H), 7.23(s, 2H), 7.17(d,J=1.8Hz,4H), 7.05~6.96(m,2H), 4.07(s,2H), 1.36(s,36H).

[0119] GN-2(diethyl10-(5'-(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinoline-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-4|4,5|4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazabolinine-2,8-dicarboxylate): A stirring bar was placed in a 250 mL 2N round-bottom flask, and a finned condenser / gas adapter and flow control were attached. The system was flushed with argon. 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) were added to the flask. The reaction mixture was vigorously stirred at room temperature for 30 seconds, after which pTsOH·H2O (0.2000 mmol, 38 mg) was added. The reaction mixture was stirred under argon at room temperature for 19 hours, after which DDQ (1,300 mmol, 295 mg) was added, followed by dry DCE (5 mL). The mixture was stirred at room temperature for 30 minutes, after which DDQ (0.5000 mmol, 114 mg) was added, followed by dry DCE (5 mL). After stirring for a further 30 minutes, oxidation was completed. Et3N (8,000 mmol, 1.1 mL) and BF3.OEt2 (12.00 mmol, 1.5 mL) were added to the reaction mixture. 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 evaporated under vacuum on 25 g of flash silica gel (bath temperature 60°C). This silica was placed in a loader and purified by flash chromatography using silica gel (330 g, equilibrated with 0% acetone / hexane, eluted with 0% (2 CV) → 20% acetone / hexane (15 CV)). The fraction containing the product was evaporated to dryness under vacuum and re-purified by direct loading onto a 220 g column using 10% DCM / hexane (dry loading). Elution was performed with 0% siRNA / DCM (2CV) → 0.2% siRNA / DCM (2CV) → fixed-composition 0.2% siRNA / DCM. The fraction containing the product was evaporated to dryness under vacuum to obtain an orange solid, 870 mg (52% yield). MS (APCI): Chemical formula: C 95 H 84 BF 14 Calculated value for N3O9 (M+H) = 1689; measured value: 1689. 11H NMR (400MHz, TCE) δ8.75(s,1H), 8.50(s,1H), 8.26(s,2H), 8.07(s,1H), 8.02(s,3H), 7.66( d,J=8.3Hz,2H), 7.53~7.44(m,1H), 7.43~7.34(m,4H), 7.27(d,J=8.1Hz, 1H), 7.21(t,J=1.8Hz,2H), 7.04~6.91(m,6H), 4.24(q,J=7.1Hz,4H), 4.1 0(s,2H), 2.62(s,6H), 2.00(s,6H), 1.30(t,J=7.1Hz,6H), 1.12(s,36H).

[0120] Synthesis procedure for RD-1 [ka]

[0121] General procedure for the synthesis of compound RD-1.1 - (E)-1-(4-isobutylphenyl)-3-(4-(trifluoromethyl)phenyl)propa-2-en-1-one: A stirring bar was attached to a 100 mL flask. Compound (4-isobutylphenyl)methyl ketone (2.0 g, 11.3 mmol) and 4-trifluoromethylbenzaldehyde (2.1 g, 11.9 mmol) were added to this flask along with EtOH (15 mL). NaOH (2.7 mL, 5 M in H2O) was added dropwise to this solution. After the addition, the reaction mixture was maintained at room temperature for 1 hour. TLC and LCMS indicated that the reaction was complete. The reaction mixture was diluted with 50 mL of H2O. The product was collected by vacuum filtration, washed with 50 mL of H2O, and then further dried by lyophilization to obtain PLC-9.1 as a white solid, which was used for the next step without further purification. 3.66g, 97% yield. MS(APCI): Chemical formula: C 20 H 19 Calculated value for F3O ([MH]-) = 332. Measured value: 332. 1H NMR(400MHz, CDCl3) 7.96(m,2H), 7.79(d,J=16.0Hz,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=7.2Hz,2H), 1.93(m,1H), 0.94(d,J=6.8Hz,6H).

[0122] General procedure for the synthesis of compound RD-1.2 - 1-(4-isobutylphenyl)-4-nitro-3-(4-(trifluoromethyl)phenyl)butan-1-one: A stirring bar was attached to a 100 mL flask. Compound RD-1.1 (2.0 g, 6.0 mmol), nitromethane (7 mL), and EtOH (7 mL) were added to this flask. KOH (67.3 mg, 1.2 mmol) was added to this mixture. The reaction mixture was degassed at room temperature and then heated to 95 °C and maintained at this temperature for 30 minutes. The reaction was monitored using LC-MS. After completion, the reaction mixture was cooled to room temperature and work-up by adding H2O (150 mL). The solution was extracted with ELISA (100 mL x 3). A small amount of NaCl was added during extraction to aid in the separation of the organic and aqueous phases. The combined organic phases were dried with anhydrous Na2SO4 and concentrated using a rotary evaporator to obtain PLC-9.2 as a brown liquid, which was used in the next step without further purification. Quantitative yield. MS(APCI): Chemical formula: C 21 H 22 Calculated value for F3NO3 ([M+H]+) = 394. Measured value: 394. 1 H NMR(400MHz,CDCl2CDCl2) 7.83(m,2H), 7.62(m,2H), 7.44(m,2H), 7.25(m,2H), 4.88(dd,J=12.8Hz,6.0Hz,1H), 4.71(dd,J=12.8Hz,8.4H z,1H), 4.29(m,1H), 3.43(qd,J=18.0Hz,7.6Hz,2H), 2.53(d,J=7.2Hz,2H), 1.87(m,1H), 0.90(d,J=7.8Hz,6H),

[0123] General procedure for the synthesis of compound RD-1.3 - 1-(4-isobutylphenyl)-4,4-dimethoxy-3-(4-(trifluoromethyl)phenyl)butan-1-one): A stirring bar was attached to a 250 mL flask. Compound RD-1.2 (2.4 g, 6.0 mmol), THF (67 mL), and MeOH (34 mL) were added to this flask. KOH (841.7 mg, 15.0 mmol) was added to this solution all at once. The solution was maintained at room temperature for 1 hour. Meanwhile, the solution of H2SO4 (8 mL) in MeOH (36 mL) was cooled to 0°C. Then, at 0°C, the previous solution was added dropwise to the H2SO4 solution using an additional funnel. After the addition, the reaction was warmed to room temperature. The reactants were maintained at room temperature for another 1 hour. LC-MS indicated that the reaction was complete. The reaction solution was poured over crushed ice and extracted with ELISA (150 ml × 3). The combined organic phase was washed with 10 wt% Na2CO3 in H2O, followed by washing with brine. After drying with anhydrous Na2SO4, the solution was concentrated under a vacuum rotary evaporator to obtain RD-1.3 as a brown oil, which was used in the next step without further purification. MS(APCI): Chemical formula: C 23 H 27 Calculated value for F3O3 ([M-OMe]+) = 378. Measured value: 378. 1 H NMR(400MHz,CDCl2CDCl2) 7.83(m,2H), 7.55(m,2H), 7.46(m,2H), 7.22(m,2H), 4.46(d,J=5.2Hz,1H), 3.78(td,J=9.2Hz,5.2Hz,1H), 3.54(dd,J=17.6Hz,4 .8Hz,1H), 3.39(dd,J=17.6Hz,8.8Hz,1H), 3.38(s,3H), 3.32(s,3H), 2.52(d,J=7.2Hz,1H), 1.88(m,1H), 0.90(d,J=6.4Hz,6H).

[0124] General procedure for the synthesis of compound RD-1.4 - 2-(4-isobutylphenyl)-4-(4-(trifluoromethyl)phenyl)-1H-pyrrole: RD-1.3 (2.5 g, 6.0 mmol) and NH4·OAc (2.2 g, 29.2 mmol) were added to a 100 ml flask in AcOH (7.2 mL). The solution was degassed at room temperature. The solution was then heated to 100 °C and maintained at this temperature for 5 hours with stirring. TLC (50% ethyl acetate in hexane) indicated that the reaction was complete. The reaction mixture was quenched by adding H2O (40 mL) and extracted with DCM (60 mL x 3). The combined organic phase was washed with saturated NaHCO3 and brine. After drying with anhydrous Na2SO4, the solution was concentrated under a rotary evaporator and purified by silica gel flash chromatography using DCM in hexane (0% → 100%) as the eluent to obtain pure compound RD-1.4 as a pale grayish-blue solid (1.6 g in 3 steps, 78% yield). MS(APCI): Chemical formula: C 21 H 20 Calculated value for F3N ([MH]-) = 343, measured value: 343. 1 H NMR(400MHz,CDCl2CDCl2) δ8.60(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=7.2Hz,1H), 1.89(m,1H), 0.93(d,J=6.4Hz,1H).

[0125] General procedure for the synthesis of compound RD-1.5 - 4-(5,5-difluoro-3,7-bis(4-isopentylphenyl)-1,9-bis(4-(trifluoromethyl)phenyl)-5H-4|4,5|4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazabolinin-10-yl)-3,5-dimethylphenol: An air condenser and stirring bar were attached to a 100 mL two-necked round-bottom flask. RD-1.4 (686.8 mg, 2.0 mmol) and 4-hydroxyl-2,6-dimethylbenzaldehyde (150.2 mg, 1.0 mmol) were added to this flask, followed by the addition of anhydrous dichloroethane (22 ml). After sparging the reaction mixture with Ar for 30 minutes, p-TsOH·H2O (34.2 mg, 0.2 mmol) was added. The reaction solution was heated to 60°C and maintained at this temperature overnight. The reaction mixture was then cooled to room temperature, and DDQ (454.0 mg, 2.0 mmol) was added. The reaction mixture was maintained at room temperature for 30 minutes. BF3·OEt2 (1.5 mL, 12.0 mmol) and Et3N (1.1 mL, 8.0 mmol) were then added at room temperature. The reaction mixture was heated to 50°C and maintained at this temperature for 2 hours. Silica gel was loaded onto the reaction mixture, and the mixture was purified by flash chromatography using DCM in hexane (0 → 100%) as the eluent to obtain pure RD-1.5 as a deep blue-violet solid (669.0 mg, 77% yield). MS(APCI): Chemical formula: C 51 H 45 Calculated value ([MH]-) for BF8N2O: 864, measured value: 864. 1 H NMR(400MHz,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=7.2Hz,4H), 1.96(s,6H), 1.93(m,2H), 0.94(d,J=6.4Hz,12H).

[0126] General procedure for the synthesis of compound RD-1 - A stirring bar was attached to a vial containing 4-(5,5-difluoro-3,7-bis(4-isobutylphenyl)-1,9-bis(4-(trifluoromethyl)phenyl)-5H-4|4,5|4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazabolinin-10-yl)-3,5-dimethylphenyl 2-(4-(1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinoline-2(3H)-yl)phenyl)acetic acid. Compounds PLC-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 to this vial, followed by the addition of anhydrous DCM (5 ml). The reaction mixture was maintained at room temperature overnight. Silica gel was loaded onto the reaction mixture and purified by flash chromatography using  in DCM (0% → 8% → 10%) as the eluent to obtain a deep reddish-purple solid. This solid was further triturated with MeOH (10 ml) to obtain RD-1 (19.0 mg, 27% yield). MS(APCI): Chemical formula: C 84 H 61 BF 11 Calculated value ([MH]-) for N3O5: 1411, measured value: 1411. 1 H NMR(400MHz,CDCl2CDCl2) 8.70(d,J=8.0Hz,1H), 8.66(d,J=8.0Hz,1H), 8.30(d,J=2.0Hz,1H), 8.12(d,J=8.0Hz,1H), 7.85(m,9H), 7.55(m,3H), 7.40(m,3H), 7.2 6(m,8H), 6.90(m,4H), 6.56(s,2H), 6.16(s,2H), 3.85(s,2H), 2.56(d,J=6.8Hz,4H), 2.04(s,6H), 1.93(m,2H), 0.94(d,J=7.4Hz,12H).

[0127] RD-2 synthesis procedure [ka]

[0128] Synthesis procedure for compound FD-4 [ka]

[0129] Compound FD-1.1(6-(2-nitrophenyl)-1H,3H-benzo[de]isochromene-1,3-dione): A mixture of 2-nitrophenol (6.6 g, 48 mmol) and KOH powder (2.4 g, 43 mmol) was mixed and stirred under vacuum for 30 minutes. Copper powder (0.4 g) was then added, followed by 100 mL of anhydrous DMF. After stirring the mixture for 5 minutes, 4-chloronaphthalic anhydride (5.1 g, 22 mmol) was added. After degassing the entire mixture, it was heated under reflux for 1.5 hours. After cooling to room temperature, 100 mL of 20% hydrochloric acid was added dropwise to the resulting reaction mixture, and it was allowed to stand for 2 hours. The precipitate was collected by filtration and dried overnight under vacuum to obtain a yellowish-brown solid (4.6 g). This was further purified by stirring in refluxed acetic acid (50 mL) for 1 hour, and then cooled to room temperature. After filtration and drying in air, a yellow solid (3.0 g, 41% yield) was obtained. Confirmed by LC-MS (APCI): C 18 H 10 Calculated value (M+H) for NO6: 336.0; Measured value: 336. 1 ¹H NMR (400MHz, chloroform-d): δ 8.80 (dd, J=8.5, 1.2Hz, 1H), 8.72 (dd, J=7.3, 1.2Hz, 1H), 8.50 (d, J=8.2Hz, 1H), 8.19 (dd, J=8.2, 1.7Hz, 1H), 7.90 (dd, J=8.5, 7.3Hz, 1H), 7.79 (td, J=7.9, 1.7Hz, 1H), 7.54 (td, J=8.0, 1.3Hz, 1H), 7.39 (dd, J=8.3, 1.2Hz, 1H), 6.89 (d, J=8.2Hz, 1H).

[0130] Compound FD-1.2(6-(2-aminophenoxy)-1H,3H-benzo[de]isochromene-1,3-dione): A mixture of compound FD-1.1 (2.0 g, 6 mmol) and iron powder (less than 10 μm, 0.91 g, 16 mmol) in acetic acid (75 mL) was heated under reflux for 30 minutes. The resulting solution was poured into water (220 mL). The resulting precipitate was collected by filtration, washed with water, and completely dried in air followed by under vacuum to obtain a yellow solid (1.65 g, 90% yield). Confirmed by LC-MS (APCI): Chemical formula C 18 H 12 Calculated value (M+H) for NO4: 306.1; Measured value: 306.

[0131] Compound FD-1.3 (1H,3H-isochromeno[6,5,4-mna]xanthene-1,3-dione): Compound FD-1.2 (1.5 g, 4.9 mmol) was dispersed in acetic acid (35 mL) and cooled to 0°C. While stirring, pre-cooled hydrochloric acid (3 mL, 37 mmol) was added, followed by the dropwise addition of sodium nitrite solution (3.29 g, 46 mmol) in 12 mL of water at 0°C. After stirring the entire mixture at 0°C for 1 hour, it was transferred to an additional funnel and added dropwise to refluxed copper sulfate solution (5.08 g, 20 mmol, in 50 mL of water) over 1 hour. After cooling to room temperature, the precipitate was collected by filtration, washed with water and acetone, and then dried in air followed by under vacuum to obtain a yellow solid (0.92 g, 65% yield). Confirmed by LC-MS (APCI): Chemical formula C 18 Calculated value (M-) for H8O4: 288.0; Measured value: 288.

[0132] Compound FD-4.1 (5,11-dibromo-1H,3H-isochromeno[6,5,4-mna]xanthene-1,3-dione): A stirring bar was placed in a 2 L 2N round-bottom flask, and a long-finned condenser was attached. Compound FD-3.1 (34.688 mmol, 10.00 g), followed by ortho-dichlorobenzene (1000 mL), was added to the flask. The reaction mixture was stirred at room temperature, and Br2 (416.26 mmol, 21.3 mL) was added. The second opening was stoppered, and the reaction mixture was heated to 75°C over the weekend, open to air, using an aluminum heat block. The reaction mixture was cooled to room temperature, and the solid was filtered off. The filtrate was diluted with hexane (approximately 20% by volume), and the second precipitate was filtered off. Both of these precipitates were dried at 100°C under vacuum. An orange-colored solid, total weight 10.866 g (69.9% yield). LC-MS and NMR were similar. MS (APCI): Chemical formula: C 18 Calculated value for H6Br2O4: (M+H) = 445; Measured value: 445. 1 H NMR(400MHz,TCE) δ9.47(dd,J=8.4,1.5Hz,1H), 8.76(d,J=14.2Hz,2H), 7.72~7.63(m,1H), 7.56(dd,J=8.3,1.4Hz,1H), 7.46(ddd,J=8.5,6.7,1.9Hz,1H).

[0133] Compound FD-4.2(2-(4-(5,11-dibromo-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinoline-2(3H)-yl)phenyl)acetic acid): A stirring bar was placed in a 100 mL 2N round-bottom flask, and a finned condenser / gas adapter and flow control were attached. The system was flushed with argon. 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) were added to the flask. 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, quenched with 6N HCl (approximately 5 mL), and diluted with water (up to approximately 350 mL). The precipitate was filtered off and washed with water. The product was dried by suction and used in the next reaction without further purification. Assume 100% yield. MS (APCI): Chemical formula: C 26 H 13 Calculated value (M+H) for Br2NO5: 578; Measured value: 578.

[0134] 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]isoquinoline-2(3H)-yl)phenyl)acetic acid): A stir bar was placed in a 250 mL 2N round-bottom flask, and a condenser / gas adapter with fins and a flow control were attached. The system was flushed with argon. To the flask were 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 several minutes, and then Pd(dppf)Cl2 (0.0245 mmol, 179 mg) was added. After the headspace was flushed with argon for 1 minute, the flow control was closed. The reaction mixture was stirred and heated at 80 °C in an aluminum heat block for 3 hours. The crude reaction mixture was evaporated to dryness in vacuo, taken up in DCM, and evaporated in vacuo over approximately 35 g of flash silica gel. Purification was by flash chromatography on silica gel (220 g, equilibrated with 0% EtOAc / DCM, eluting with 0% (10 CV) → 15.3% EtOAc / DCM (15.3 CV) → 40% EtOAc / DCM (10 CV) → isocratic 40% EtOAc / DCM). EtOAc contained 0.1 volume % TFA, and 1.710 g (57.6% yield) of a pale yellow solid was obtained. MS (APCI): Calculated for C 42 H 19 F 12 For NO5 calculated (M + H) = 846; found: 846. 1 H 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).

[0135] Compound RD-2.1((E)-1-(4-isobutylphenyl)-3-phenylpropa-2-en-1-one): A stirring bar was placed in a 500 mL round-bottom flask. 1-(4-isobutylphenyl)ethane-1-one (19.57 mmol, 3.540 g) and benzaldehyde (19.57 mmol, 2.077 g) were added to the flask. 200 proof ethanol (10 mL) was added to the flask, and the solution was stirred to obtain a clear solution. Water (4.70 mL) was added to the flask, followed by 5 N 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 (approximately 100 mL), the resulting precipitate was filtered off, and washed with water. The crude solid was dried overnight under vacuum at room temperature to obtain a grayish-white solid, 4.844 g (94% yield). MS(APCI): Chemical formula C 19 H 20 Calculated value for O: (M+H) = 265; Measured value: 265. 1 H NMR(400MHz,TCE) δ7.99~7.92(m,2H), 7.80(d,J=15.7Hz,1H), 7.71~7.64(m,2H), 7.56(d,J=15.7Hz,1H), 7.45(p,J=3. 5Hz,3H), 7.34~7.28(m,2H), 2.57(d,J=7.2Hz,2H), 1.92(hept,J=6.8Hz,1H), 0.93(d,J=6.6Hz,6H).

[0136] Compound RD-2.3(1-(4-isobutylphenyl)-4-nitro-3-phenylbutan-1-one): A 500 mL eggplant flask was charged with compound RD-2.2 (18.323 mmol, 4.844 g) and a stir bar. Nitromethane (15 mL) and 200 proof ethanol (15 mL) were added to the flask. The mixture was stirred to obtain a clear solution, and then KOH (2.346 mmol, 137 mg) was added. A condenser with a fin was added, and the reaction mixture was heated at 95 °C for 2 h in an aluminum heat block. The crude reaction mixture was partitioned between EtOAc (ca. 125 mL) and water (ca. 125 mL). The layers were separated, the organic layer was washed with water (1 × 50 mL), dried over MgSO4, filtered, and evaporated to dryness in vacuo to afford a brown oil (which solidified very slowly at room temperature), 5.753 g (97% yield). MS (APCI): calculated for C 20 H 23 NO3 (M+H) = 326; found: 326. 1 H 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).

[0137] Compound RD-2.5 (2-(4-Isobutylphenyl)-4-phenyl-1H-pyrrole) (1655-52): A stirring bar was placed in a 500 mL round-bottom flask. The system was flushed with argon. Compound RD-2.3 (17.670 mmol, 5.570 g), dry THF (200 mL), and dry methanol (100 mL) were added to the flask. The reaction mixture was stirred at room temperature to obtain a clear solution. KOH (45.765 mmol, 2.568 g) was added to the flask, and the reaction mixture was stirred at room temperature for 1 hour. A stirring bar was placed in a 1 L 2N round-bottom flask, and a flow control, addition funnel, and gas adapter were attached. The system was flushed with argon. Dry MeOH (100 mL) was added to the flask, and the reaction mixture was cooled to 0°C. 96% H2SO4 (22 mL) (exothermic) was carefully added to this flask. Once the reaction mixture had cooled again to 0°C, the first solution was transferred to an additive funnel and added to the MeOH / H2SO4 mixture over 30 minutes. The mixture was stirred at 0°C for 30 minutes, then at room temperature for 2 hours. The reaction mixture was poured over approximately 250 mL of crushed ice and diluted with toluene (approximately 100 mL). The mixture was transferred to a separatory funnel, and the emulsion was broken up by adding some NaCl. The layers were separated, the aqueous layer was extracted with toluene (1 × 100 mL), the combined organic layers were washed with brine (1 × 50 mL), dried over MgSO4, filtered, and evaporated to obtain a brown oil. This oil was transferred to a 500 mL round-bottom flask and a stirring bar was added. Ammonium acetate (85.88 mmol, 6.619 g) was added to the flask, followed by acetic acid (30 mL). A finned condenser was added to the flask, the reaction mixture was stirred, and the mixture was heated overnight at 100°C in an aluminum heat block. The mixture was cooled to room temperature and diluted with water (approximately 200 mL). The resulting precipitate was filtered and washed with water. The precipitate was dissolved in DCM, separated from water, dried over MgSO4, filtered, and evaporated under vacuum on approximately 60 g of flash silica gel. This silica gel was transferred to a loader and purified by flash chromatography on silica gel (120 g, equilibrated with 0% siRNA / hexane, eluted with 0% (2 CV) → 20% siRNA / hexane (20 CV)). The fraction containing the product was evaporated to dryness under vacuum to obtain a purplish-blue solid, 2.981 g (59.2% to 61% yield of compound). MS(APCI): Chemical formula C.20 H 21 Calculated value for N: (M+H) = 276; Measured value: 276. 1 H NMR(400MHz,TCE) δ8.51(s,1H), 7.61~7.55(m,2H), 7.48~7.42(m,2H), 7.38(t,J=7.7Hz,2H), 7.26~7.17(m,3H), 7.16(dd,J=2.7, 1.7Hz,1H), 6.80(dd,J=2.8,1.7Hz,1H), 2.50(d,J=7.2Hz,2H), 1.89(hept,J=6.8Hz,1H), 0.93(d,J=6.6Hz,6H).

[0138] Compound RD-2.6(4-(5,5-difluoro-3,7-bis(4-isobutylphenyl)-1,9-diphenyl-5H-4|4,5|4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazabolinin-10-yl)-3,5-dimethylphenol)(1655-56): Compound RD-2.6 was synthesized from compound RD-2.5 (2.00 mmol, 551 mg), 4-hydroxy-2,6-dimethylbenzaldehyde (1.00 mmol, 150 mg), and pTsOH·H2O (0.300 mmol, 57 mg), and then from DDQ (1.70 mmol, 386 mg), 2×Et3N (8.000 mmol, 1.12 mL), and BF3·OEt2 (12.00 mmol, 1.48 mL) in dry DCE (50 mL), at 60°C, and then at 50°C. The crude reaction mixture was diluted with approximately 10 mL of hexane, loaded onto approximately 30 g of flash silica gel in a loader, and purified by flash chromatography on silica gel (120 g, equilibrated with 0% siRNA / hexane, eluted with 0% (2 CV) → 20% siRNA / hexane (20 CV)). The fraction containing the product was evaporated to dryness under vacuum to obtain a deep red solid, 219 mg (30% yield). MS(APCI): Chemical formula C 49 H 47 Calculated value for BF2N2O: (M+H) = 729; measured value: 729. 1H NMR(400MHz,TCE) δ7.87(d,J=8.1Hz,4H), 7.26(d,J=8.2Hz,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=7.1Hz,4H), 2.03~1.84(m,8H), 0.94(d,J=6.6Hz,12H).

[0139] Compound RD-2(4-(5,5-difluoro-3,7-bis(4-isobutylphenyl)-1,9-diphenyl-5H-4|4,5|4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazabolinin-10-yl)-3,5-dimethylphenyl 2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinoline-2(3H)-yl)phenyl)acetate): Compound RD-1 was synthesized in the same manner as compound RD-2.2 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). The crude reaction mixture was diluted with hexane and loaded onto approximately 20 g of flash silica gel in a loader. The mixture was purified by flash chromatography on silica gel (equilibriumized with 120 g, 0% siRNA / DCM, eluted at 0% constant composition). The fraction containing the product was evaporated to dryness under vacuum to obtain a deep red solid, 62 mg (73% yield). MS(APCI): Chemical formula C 91 H 64 BF 14 Calculated value for N3O5: (M+H) = 1556; Measured value: 1556. 1H NMR(400MHz,TCE) δ8.78(s,1H), 8.52(s,1H), 8.32~8.24(m,2H), 8.08(s,1H), 8.03(s,3H), 7.88(d,J=8.0Hz,4H) , 7.60(d,J=8.3Hz,2H), 7.49(ddd,J=8.5,6.1,2.7Hz,1H), 7.41(d,J=8.3Hz,2H), 7.27(dd,J=7 .8,4.7Hz,5H), 7.07~6.88(m,8H), 6.78(dt,J=6.7,1.5Hz,4H), 6.51(s,2H), 6.09(s,2H), 3.90 (s,2H), 2.55(d,J=7.1Hz,4H), 2.05(s,6H), 1.92(hept,J=6.6Hz,2H), 0.95(d,J=6.6Hz,12H).

[0140] Synthesis procedure for compound RD-3 [ka]

[0141] General procedure for the synthesis of compound RD-3.2 - 4-(3,7-bis(4-bromophenyl)-5,5-difluoro-1,9-diphenyl-5H-4|4,5|4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazabolinin-10-yl)-3,5-dimethylphenol: An air condenser and stirring bar were attached to a 100 mL two-necked round-bottom flask. RD-3.1 (synthesized according to 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 to the flask, followed by the addition of anhydrous dichloroethane (35 ml). The reaction mixture was sparged with Ar for 30 minutes, after which p-TsOH·H2O (57.3 mg, 0.30 mmol) was added. The reaction solution was heated to 60°C and maintained at this temperature overnight. The reaction mixture was then cooled to room temperature, and DDQ (608.4 mg, 2.68 mmol) was added. The reaction mixture was maintained at room temperature for 30 minutes. Next, 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 to 50°C and maintained at this temperature for 2 hours. The reaction mixture was loaded onto silica gel and purified by flash chromatography using DCM in hexane (0% → 100%) as the eluent to obtain pure RD-3.2 as a dark purple to golden solid (560.0 mg, 43% yield). MS(APCI): Chemical formula C 41 H 29 Calculated values ​​for BBr2F2N2O ([MH] - )=774, measured value: 774. 1 H NMR(400MHz,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).

[0142] General procedure for the synthesis of compound RD-3.3 - 3,3'-((5,5-difluoro-10-(4-hydroxy-2,6-dimethylphenyl)-1,9-diphenyl-5H-4|4,5|4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazabolinine-3,7-diyl)bis(4,1-phenylene))bis(propa-2-in-1-ol): A stirring bar was attached to a 100 mL Schlenk 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 propa-2-in-1-ol (44.8 mg, 0.8 mmol) were added to this tube, followed by the addition of anhydrous Et3N (5 ml). The reaction mixture was sparged with N2 for 30 minutes. The reaction mixture was heated to 80°C and maintained at this temperature for 8 hours. LC-MS indicated that the reaction was complete. DCM (50 ml) and 0.5 M HCl (100 mL) were added. The aqueous phase was further extracted with DCM (50 ml x 3). The combined organic phases were concentrated under a rotary evaporator, and the crude product was purified by flash chromatography using toluene (0% → 50%) in DCM as the eluent to obtain pure RD-3.3 as a dark purple solid (111.0 mg, 77% yield). MS(APCI): Chemical formula C 47 H 35 Calculated values ​​for BF2N2O3 ([MH] - )=724, measured value:724. 1 H NMR(400MHz,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=6.0Hz,4H), 4.27(s,1H), 1.98(s,6H), 1.77(t,J=6.0Hz,2H).

[0143] General procedure for the synthesis of compound RD-3 - ((10-(4-(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinoline-2(3H)-yl)phenyl)acetoxy)-2,6-dimethylphenyl)-5,5-difluoro-1,9-diphenyl-5H-4|4,5|4-dipyrrolo[1,2-c:2 ',1'-f][1,3,2]diazabolinine-3,7-diyl)bis(4,1-phenylene))bis(propa-2-in-3,1-diyl)bis(2-(4-(5,11-bis(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinoline-2(3H)-yl)phenyl)acetate): A stirring bar was attached to a 25 mL vial. Compounds 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 to the vial, followed by the addition of anhydrous DCM (11 ml). The reaction mixture was maintained at room temperature overnight. The reaction mixture was loaded onto silica gel and purified by flash chromatography using Âr (0% → 10%) from DCM as the eluent to obtain RD-3 as a dark reddish-purple solid. The solid was further triturated with Âr / MeOH (2 ml / 10 ml) to obtain RD-3. The solid was further purified by flash chromatography using toluene in hexane (0% → 60%) and toluene in DCM (0% → 10%) as eluents, and then tritulated with DCM / toluene / MeOH (9:1:10). This cycle was repeated twice to obtain pure RD-3 (163.0 mg, 73% yield). 1H NMR(400MHz,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).

[0144] Synthesis of additional RD-3 [ka]

[0145] Compound 9.1 (5,11-dibromo-1H,3H-isochromeno[6,5,4-mna]xanthene-1,3-dione): A stirring bar was placed in a 2 L 2N round-bottom flask, and a long-finned condenser was attached. 1H,3H-isochromeno[6,5,4-mna]xanthene-1,3-dione (synthesized according to reference: RSC Adv., 2014, 4, 53072-53078) (34.688 mmol, 10.00 g) was added to the flask, 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 opening was stoppered, and the reaction mixture was heated to 75°C over the weekend using an aluminum heat block, with the air exposed. The reaction mixture was cooled to room temperature, and the solid was filtered off. The filtrate was diluted with hexane (approximately 20% by volume), and the second precipitate was filtered off. Both of these precipitates were dried at 100°C under vacuum. An orange-colored solid, total weight 10.866 g (69.9% yield). LC-MS and NMR were similar. MS(APCI): Chemical formula: C 18 Calculated value for H6Br2O4: (M+H) = 445; Measured value: 445. 1H NMR(400MHz,TCE) δ9.47(dd,J=8.4,1.5Hz,1H), 8.76(d,J=14.2Hz,2H), 7.72~7.63(m,1H), 7.56(dd,J=8.3,1.4Hz,1H), 7.46(ddd,J=8.5,6.7,1.9Hz,1H).

[0146] Compound 9.2(2-(4-(5,11-dibromo-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinoline-2(3H)-yl)phenyl)acetic acid): Compound 82.1 (1655-19) was synthesized at 160°C in the same manner as for compound 32.1 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) in the same manner as for compound 32.1. The crude reaction mixture was cooled to 0°C, quenched with 6N HCl (approximately 5 mL), and diluted with water (up to approximately 350 mL). The precipitate was filtered off and washed with water. The product (10.2) was dried by suction and used in the next reaction without further purification. Assume a 100% yield. MS(APCI): Chemical formula: C 26 H 13 Calculated value (M+H) for Br2NO5: 578; Measured value: 578.

[0147] 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 by heating a mixture of 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) at 80 °C under an argon atmosphere overnight. The crude reaction mixture was evaporated to dryness in vacuo, taken up in DCM, and evaporated in vacuo on approximately 35 g of flash silica gel, and purified by flash chromatography on silica gel (220 g, equilibrated with 0% EtOAc / DCM, eluting with 0% (10 CV) → 15.3% EtOAc / DCM (15.3 CV) → 40% EtOAc / DCM (10 CV) → isocratic 40% EtOAc / DCM). EtOAc contained 0.1% v / v TFA. The fractions containing the product were evaporated to dryness in vacuo to afford 2.000 g of a brownish-yellow solid (80.3% from Compound 80.1 (1655-11)). MS (APCI): Calculated for C 40 H 21 F6NO5 (M+H) = 710; Found: 710. 1 H 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).

[0148] Scheme for the synthesis of Compound 11

Chemical Structure

[0149] Compound 11.1 General Procedure for Synthesis - 4-(3,7-bis(4-bromophenyl)-5,5-difluoro-1,9-diphenyl-5H-4|4,5|4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazabolinin-10-yl)-3,5-dimethylphenol: An air condenser and stirring bar were attached to a 100 mL two-necked round-bottom 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 to this flask, followed by the addition of anhydrous dichloroethane (35 ml). After sparging the reaction mixture with Ar for 30 minutes, p-TsOH·H2O (57.3 mg, 0.30 mmol) was added. The reaction solution was heated to 60°C and maintained at this temperature overnight. The reaction mixture was then cooled to room temperature, and DDQ (608.4 mg, 2.68 mmol) was added. The reaction mixture was maintained at room temperature for 30 minutes. BF3·OEt2 (2.5 mL, 20.1 mmol) and Et3N (1.9 mL, 13.4 mmol) were then added at room temperature. The reaction mixture was heated to 50°C and maintained at this temperature for 2 hours. The reaction mixture was loaded onto silica gel and purified by flash chromatography using DCM in hexane (0% → 100%) as the eluent to obtain pure 12,1 as a dark purple to golden solid (560.0 mg, 43% yield). MS(APCI): Chemical formula C 41 H 29 Calculated values ​​for BBr2F2N2O ([MH] - )=774, measured value: 774. 1 H NMR(400MHz,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).

[0150] General procedure for the synthesis of Compound 11.2 - 3,3’-((5,5-difluoro-10-(4-hydroxy-2,6-dimethylphenyl)-1,9-diphenyl-5H-4|4,5|4-dipyrrolo[1,2-c:2’,1’-f][1,3,2]diazaborinin-3,7-diyl)bis(4,1-phenylene))bis(prop-2-yn-1-ol): A stir bar was placed in a 100 mL Schlenk tube. To this tube were added 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), followed by the addition of anhydrous Et3N (5 ml). The reaction mixture was sparged with N2 for 30 minutes. The reaction mixture was heated to 80 °C and maintained at this temperature for 8 hours. Completion of the reaction was indicated by LCMS. 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 phases were concentrated under a rotary evaporator, and the crude product was purified by flash chromatography using EtOAc in DCM (0% → 50%) as the eluant to obtain pure 12.2 as a dark purple solid (111.0 mg, 77% yield). MS (APCI): Calculated for C 47 H 35 BF2N2O3 ([M-H] - ) = 724, found: 724. 1 H 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).

[0151] Scheme for the synthesis of Compound RD-3

Chemical Structure

[0152] General procedure for the synthesis of compound RD-3 - ((10-(4-(2-(4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinoline-2(3H)-yl)phenyl)acetoxy)-2,6-dimethylphenyl)-5,5-difluoro-1,9-diphenyl-5H-4|4,5|4-dipyrrolo[1,2-c:2',1'-f][1 A stirring bar was attached to a 25 mL vial of 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 to this vial, followed by the addition of anhydrous DCM (11 ml). The reaction mixture was maintained at room temperature overnight. Silica gel was loaded into the reaction mixture and purified by flash chromatography using Âr in DCM (0→10%) as the eluent to obtain RD-3 as a deep reddish-purple solid. This solid was further triturated with Âr / MeOH (2 ml / 10 ml) to obtain RD-3. The solid was further purified by flash chromatography using Âr in hexane (0→60%) and Âr in DCM (0→10%) as the eluents, and then triturated with DCM / Âr / MeOH (10:1:10). The cycle was repeated twice to obtain pure RD-3. 139.0 mg, 71% yield. 1 H NMR(400MHz,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).

[0153] Preparation of red and / or green light-emitting inkjet inks Preparation of 25% PMMA polymer solution A commercially available eco-solvent inkjet ink (STS Inks, eco-solvent, transparent, [transparent ink using an extremely mild solvent containing 2-ethoxyethyl ether], product number SB.UMS.3000, STS inks, Boca Raton, Florida, USA) was modified to create an inkjet ink containing the above-mentioned fluorescent compound. 5% by weight of polystyrene (Aldrich, 331651-500G, Mw=35,000) was added to the ink to increase its solid content. Detailed green and red ink formulations are shown in Table 1 below.

[0154] [Table 2]

[0155] Preparation of dye-polymer solutions Printer ink cartridges (Dimatix Materials Cartridges, SAMBA) were used. Each cartridge contains a print head, has an ejection volume of 2.4 pL, and a native resolution of 75 DPI. The ink prepared above was filtered through a 0.2 micrometer filter (PTFE Acrodisc cr, PALL) and then inserted into each cartridge.

[0156] The substrate was SBL7 (8 mil general-purpose matte finish backlit film, vendor: Magic).

[0157] A high-precision material inkjet printer, the Dimatix DMP-2830 (Fujifilm), was used in combination with the aforementioned filled printer cartridge. The printer plate temperature was set to 40°C, and the cartridge temperature was set to 30°C using the cartridge's default settings. A color pixelated substrate was created using an ejection interval set to 10 mm.

[0158] Characterization of dye compounds Absolute quantum yield of dyes The quantum yield of the printed film was measured at a wavelength of 450 nm using an absolute PL quantum yield spectrometer C11347 (Hamamatsu Photonics).

[0159] Characterization of blue light conversion WLC film External quantum yield of WLC film in LED backlight devices The external quantum yield and other optical properties of WLC films in LED backlit display applications were tested using a test apparatus configured as shown in Figure 3. The blue LED edge-lit backlight was part of a Kindle device. MCPD stands for Multi-Channel Photon Detection (MCPD-9800, Otsuka Electronics Co., Ltd.).

[0160] EQE is the formula: EQE = Number of photons 500~800nm,w / WLC / ( Number of photons 400~500nm,wout / WLC - Number of photons 400~500nm,w / WLC ) It is calculated based on the following.

[0161] Color gamut - BT.2020 ratio A color gamut is a specific, complete subset of colors. A color gamut can be represented by a triangle in a chromaticity diagram. The three angles of the triangle represent the primary colors. The more colors a display can show, the larger the area of ​​the triangle, and therefore the wider the color gamut. BT.2020 is the color gamut standard for UHD projectors and televisions recommended by the ITU (International Telecommunication Union).

[0162] The optical spectra measured using the configuration shown in Figure 3 were converted into the color gamut triangles of the CIE 1931 chromaticity diagram. The area of ​​the triangles was then estimated and divided by the area of ​​the BT.2020 triangle to obtain the BT.2020 ratio as referred to herein. A larger ratio indicates a wider color gamut for the WLC film. To achieve a wide color gamut, the emission spectral shape of each primary color must be as narrow as possible. A narrow spectral shape can be characterized by a small FWHM of the emission spectrum.

[0163] When used herein, unless otherwise specified, the use of ordinal adjectives such as “first” and “second” to describe common objects merely indicates that different instances of similar objects are being referred to, and is not intended to imply that the objects described in this way must be in a given order, temporally, spatially, in terms of hierarchy, or in any other manner.

[0164] The use of "may" or "may be" or "can" should be interpreted as an abbreviation of "is" or "is not," or "does" or "does not," or "will" or "will not." For example, the statement "The film may comprise / include" should be interpreted as, for example, "In some embodiments, the film includes scattering centers located within the polymer matrix" or "In some embodiments, the film does not include scattering centers located within the polymer matrix."

[0165] Unless otherwise indicated, all numbers expressing quantities of ingredients, molecular weights, reaction conditions, and so forth used in this specification and the examples are to be understood as being modified in all instances by the term "about." The term "about" as used herein can include any numerical value that can 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" can refer to plus or minus 10% of the recited number.

[0166] Therefore, unless otherwise indicated, the numerical parameters set forth in this specification and the appended examples are approximations that can 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, each numerical parameter should at least be construed in light of the reported significant digits and by applying ordinary rounding techniques in the context of the embodiments.

[0167] For the disclosed processes and / or methods, the functions performed in the processes and methods can be implemented in various orders as may be shown by the context. Further, the described steps and operations are provided only as examples, and some steps and operations can be optional, combined into fewer steps and operations, or expanded into additional steps and operations.

[0168] The present disclosure sometimes describes different other components that are included within or associated with different other components. Such recited components are merely exemplary, and many other configurations that achieve the same or similar functions can be implemented.

[0169] In general, the terms used in this disclosure and the accompanying embodiments (e.g., the text of the accompanying embodiments) are intended to be “open” terms (for example, the term “including” should be interpreted as “including, but not limited to,” the term “having” should be interpreted as “having at least,” and the term “includes” should be interpreted as “includes, but is not limited to,” etc.). Furthermore, where a certain number of elements are introduced, this can be interpreted as including at least the number stated, as may be indicated by the context (for example, the literal description of “two descriptions” without other modifiers includes at least two descriptions or two or more descriptions). Any disjunctions and / or disjunctions that, when used in this disclosure, represent two or more alternative terms should be understood to construed as construing the possibility of including one of the terms, either of the terms, or both of the terms. For example, the phrase "A or B" would be understood to include the possibilities of "A" or "B" or "A and B".

[0170] The terms and words used herein are not limited to their bibliographic meanings but are used solely to enable a clear and consistent understanding of the invention. The terms “a,” “an,” “the,” and similar references used in the context describing this disclosure (particularly in the context of the following embodiments) should be interpreted as including both singular and plural forms unless otherwise specifically indicated herein or unless the context clearly contradicts this interpretation. Any examples or representative phrases (e.g., “such as”) provided herein are intended solely to better illustrate this disclosure and do not imply any limitation on the scope of any embodiment. The language used herein should not be interpreted as referring to any unexpressed elements essential to the implementation of this disclosure.

[0171] The grouping of alternative elements or embodiments disclosed herein should not be construed as limiting. Members of each group may be referenced and embodied individually or in any combination with other members of the group or other elements found herein. For convenience and / or patentability reasons, it is anticipated that one or more members of a group may be included in or removed from a group. If such inclusion or removal occurs, this specification will include the modified groups and will therefore satisfy the description of all Markush groups used in the accompanying embodiments.

[0172] Certain embodiments described herein include the best mode known to the inventors for carrying out the disclosure. Naturally, variations of these described embodiments will be apparent to those skilled in the art by reading the above description. The inventors anticipate that those skilled in the art will use such variations as needed, and they intend that the disclosure will be carried out in ways other than those specifically described herein. Thus, embodiments include all variations and equivalents of the subject matter described in the embodiments, as permitted by applicable law. Furthermore, unless otherwise specifically indicated herein, or unless it is clearly inconsistent with the context, all combinations of the above elements in all possible variations are contemplated. Finally, it should be understood that the embodiments disclosed herein are illustrative of the principles of the embodiments. Other variations that may be used are within the scope of the embodiments. Thus, alternative embodiments may be used, for example, in accordance with the teachings herein, but not limited thereto. Thus, embodiments are not limited to those strictly shown and described.

[0173] The term "substantially" means that the features, parameters, or values ​​mentioned do not need to be realized exactly, and that deviations or variations, including, for example, tolerances, measurement errors, limitations on measurement accuracy, and other factors known to those skilled in the art, may occur to the extent that they do not preclude the effect that the features are intended to produce.

[0174] The embodiments of this disclosure can be embodied in other forms without departing from their essence or essential features. The embodiments described should be considered in all respects to be illustrative and not restrictive. The embodied subject matter is shown by the appended embodiments rather than by the foregoing description. All modifications that fall within the meaning and scope of equivalence of embodiments are encompassed within that scope.

Claims

1. A wavelength conversion medium, Ink media and, At least one blue-absorbing compound, A first photoluminescent dye comprising a portion that absorbs blue wavelength light and a portion that emits light over a narrow range, A wavelength conversion medium comprising the blue absorption compound and the first photoluminescence dye, wherein the blue absorption compound and the first photoluminescence dye are disposed within the ink medium.

2. The wavelength conversion medium according to claim 1, wherein green wavelength light having an emission spectrum with a full width at half maximum of less than 40 nm can be emitted from the portion that emits within the narrow range.

3. The wavelength conversion medium according to claim 2, wherein the portion emitting within the narrow range has an emission peak in the range of approximately 520 nm to approximately 535 nm.

4. The wavelength conversion medium according to claim 1, wherein red wavelength light having an emission spectrum with a full width at half maximum of less than 55 nm can be emitted from the portion that emits within the narrow range.

5. The wavelength conversion medium according to claim 4, wherein the portion emitting within the narrow range has an emission peak in the range of approximately 610 nm to approximately 650 nm.

6. The wavelength conversion medium according to claim 1, further comprising one or more scattering centers, wherein the scattering centers are located within the ink medium.

7. The wavelength conversion medium according to claim 1, wherein the ink medium includes a transparent ink substrate.

8. The wavelength conversion medium according to claim 1, further comprising a FRET dye which is a sharp emitter.

9. The wavelength conversion medium according to claim 8, wherein the FRET dye, which is a sharp emitter, comprises a second blue-absorbing compound.

10. The aforementioned blue-absorbing compound is given by the following formula: 【Chemistry 1】 (In the formula, R １ is arylcarboxy, C ４～８ Alkyl, or C ４～１０ It is alkyl, R ２ , R ３ , and R ４ The wavelength conversion medium according to claim 1, wherein is a compound (selected independently from H or tetrahalogen-substituted aryl).

11. R １ but, 【Chemistry 2】 or 【Transformation 3】 A wavelength conversion medium according to claim 10, selected from the following.

12. R ２ 、R ３ 、 or R ４ is H, 【Chemistry 4】 or 【Transformation 5】 A wavelength conversion medium according to claim 10, independently selected from the above.

13. The aforementioned blue absorber compound is the following compound: 【Transformation 6】 【Transformation 7】 【Transformation 8】 The wavelength conversion medium according to claim 10, which is one of the above.

14. The first photoluminescent dye is the following compound: 【Chemistry 9】 【Chemistry 10】 【Chemistry 11】 【Chemistry 12】 【Chemistry 13】 A wavelength conversion medium according to claim 1, which is one of the following.

15. The wavelength conversion medium according to any one of claims 1 to 14, wherein the wavelength conversion medium has an internal quantum yield of more than 80%.

16. The wavelength conversion medium according to any one of claims 1 to 14, wherein the wavelength conversion medium has an external quantum yield of more than 50%.

17. The wavelength conversion medium according to any one of claims 1 to 14, wherein the wavelength conversion medium has a color gamut exceeding 90% of the BT. 2020 standard.

18. The wavelength conversion medium according to any one of claims 1 to 14, wherein the wavelength conversion medium has a thickness of less than 100 μm.

19. A printing layer comprising a wavelength conversion medium according to any one of claims 1 to 14, wherein blue light is absorbable by the printing layer, and the blue light is convertible by the printing layer into green light or red light having a sharp emission spectrum.

20. The printing layer according to claim 19, further comprising a transparent substrate.

21. The printed layer according to claim 19, wherein at least a portion of the wavelength conversion medium is provided as a plurality of dots located across predetermined pixel positions of a light-emitting device.

22. The printed layer according to claim 21, wherein the plurality of dots are sized to cover predetermined pixel positions of the light-emitting device.

23. A light-emitting device comprising a wavelength conversion medium according to any one of claims 1 to 14.

24. A backlit device having a blue light source, comprising a wavelength conversion medium according to any one of claims 1 to 14.

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