JP2024508226A - Boron-containing cyclic releasing compound and color conversion film containing the same - Google Patents

Abstract

The present disclosure relates to novel photoluminescent complexes containing a BODIPY moiety covalently bonded to a blue light-absorbing xantenoisoquinoline derivative, and color conversion films and backlight units using the same. [Selection diagram] None

Description

[Cross reference to related applications]
This application claims priority to U.S. Provisional Patent Application No. 63/152,301, filed February 22, 2021, and is incorporated herein by reference in its entirety.

In color reproduction, a gamut is a certain complete subset of colors available on a device such as a television or monitor. For example, Adobe(TM) Red Green Blue (RGB), a wide gamut color space achieved by using pure spectral primaries, provides a wider color gamut and allows for more visible colors seen through a display. Developed to bring realistic expression. It is believed that devices that can provide a wider color gamut may enable displays to portray more vivid colors.

As high-definition large-screen displays become more common, demand for higher performance, thinner, and more functional displays is increasing. Modern light emitting diodes (LEDs) are obtained by a blue light source exciting a green, red, or yellow phosphor to obtain a white light source. However, the full width at half maximum (FWHM) of the emission peak of current green and red phosphors is very large, typically exceeding 40 nm, resulting in color rendering where the green and red spectra overlap and cannot be completely distinguished from each other. is brought about. This overlap leads to poor color rendering and reduced color gamut.

To compensate for the loss of color gamut, methods have been developed to use films containing quantum dots in combination with LEDs. However, there are problems with using quantum dots. First, cadmium-based quantum dots are highly toxic and have been banned in many countries due to health safety concerns. Second, non-cadmium-based quantum dots have very low efficiency in converting blue LED light into green and red light. Third, quantum dots require expensive encapsulation processes to protect them from moisture and oxygen. Finally, the cost of using quantum dots is high due to the difficulty in controlling size uniformity during the manufacturing process.

Therefore, a need exists to improve performance in color conversion films, backlight units, and display devices.

The photoluminescent complexes described herein can be used to improve the contrast between discernible colors in televisions, computer monitors, smart devices, and any other device that utilizes color displays. The photoluminescent complexes of the present disclosure have good blue light absorption and narrow emission bandwidth, providing novel color converting dye complexes with full width at half maximum (FWHM) of the emission band less than 40 nm. In some embodiments, the photoluminescent complex absorbs light at a first wavelength and emits light at a second wavelength that is higher than the first wavelength. The photoluminescent complexes disclosed herein can be utilized in color conversion films used in light emitting devices. The color conversion film of the present disclosure reduces color degradation by reducing overlap in the color spectrum, resulting in high quality color rendition.

Some embodiments include a photoluminescent complex, the photoluminescent complex comprising a blue light absorbing xanthenoisoquinoline derivative and a linker complex comprising an optionally substituted ester or an optionally substituted ether; boron-dipyrromethene (BODIPY) moieties. In some embodiments, the linker conjugate can covalently attach the xanthenoisoquinoline derivative to the BODIPY moiety. In some embodiments, the xanthenoisoquinoline derivative absorbs light at the first excitation wavelength and transfers energy to the BODIPY moiety. In some embodiments, the BODIPY moiety absorbs energy from the xanthenoisoquinoline derivative and emits light energy at a second, higher wavelength. In some embodiments, the photoluminescent complex has an emission quantum yield greater than 80%.

In some embodiments, the photoluminescent complex may have an emission band with a full width at half maximum (FWHM) of up to 40 nm.

In some embodiments, the photoluminescent complex may have a Stokes shift, ie, the difference between the excitation peak of the blue light absorption moiety and the emission peak of the BODIPY moiety, of 45 nm or more.

（式中、Ｒ^０及びＲ^１０は、独立して、水素（Ｈ）、Ｃ_１～Ｃ_４アルキル基、又は任意に置換されたアリール基であり得る）のものであり得る。 In some embodiments, the xanthenoisoquinoline derivative has the following general formula:

(wherein R ⁰ and R ¹⁰ can independently be hydrogen (H), a C ₁ -C ₄ alkyl group, or an optionally substituted aryl group).

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６は、独立して、水素原子（Ｈ）、Ｃ_１～Ｃ_３アルキル基、任意に置換されたアリール基又はエーテル基から選択される）のものであり得る。幾つかの実施の形態においては、Ｒ^７、Ｒ^８、及びＲ^９は、独立して、水素原子（Ｈ）、メチル基（－ＣＨ_３）、又は－Ｃｌから選択され得る。 In some embodiments, the BODIPY moiety has the following general formula:

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are independently a hydrogen atom (H), a C ₁ to C ₃ alkyl group, an optionally substituted aryl group, or an ether (selected from the group). In some embodiments, R ⁷ , R ⁸ , and R ⁹ may be independently selected from a hydrogen atom (H), a methyl group (-CH ₃ ), or -Cl.

Some embodiments include a color conversion film. In some examples, the color conversion film can include a color conversion layer that includes a resin matrix and at least one photoluminescent complex described herein dispersed within the resin matrix. In some embodiments, the color conversion film can have a thickness between about 1 μm and about 200 μm. In some embodiments, the color conversion film of the present disclosure can absorb blue light in a wavelength range of about 400 nm to about 480 nm and emit light in a wavelength range of about 510 nm to about 560 nm. Another embodiment includes a color conversion film capable of absorbing blue light in a wavelength range of about 400 nm to about 480 nm and emitting light in a wavelength range of about 575 nm to about 645 nm. In some embodiments, the color conversion film may further include a transparent substrate layer. In some embodiments, the transparent substrate layer includes two opposing surfaces and the color conversion layer is disposed on one of the opposing surfaces.

Some embodiments include a method of making a color conversion film. In some embodiments, the method includes dissolving the aforementioned photoluminescent complex and a binder resin in a solvent and applying the mixture to one of the opposing surfaces of the transparent substrate.

Some embodiments include a backlight unit that includes a color conversion film as described herein.

Some embodiments include a display device that includes a backlight unit as described herein.

The present application provides a photoluminescent complex with excellent color gamut and luminescent properties, a method of manufacturing a color conversion film using the photoluminescence complex, and a backlight unit equipped with the color conversion film. These and other embodiments are described in more detail below.

1 is a graph showing the absorption and emission spectra of one embodiment of a photoluminescent complex (PLC-1). 1 is a graph showing the absorption and emission spectra of one embodiment of a photoluminescent complex (PLC-2). 1 is a graph showing the absorption and emission spectra of one embodiment of a photoluminescent complex (PLC-4). 1 is a graph showing the absorption and emission spectra of one embodiment of a photoluminescent complex (PLC-5).

The present disclosure relates to photoluminescent compounds and complexes used in color conversion films, backlight units, and display devices.

In some embodiments, the present disclosure includes photoluminescent complexes and their use in color conversion films. Photoluminescent complexes can be used to improve and enhance transmission of one or more desired emission bandwidths within a color conversion film. In some embodiments, the photoluminescent complex can also enhance transmission of a desired first emission bandwidth while decreasing transmission of a second emission bandwidth. For example, color conversion films can enhance the contrast or intensity between two or more colors to increase their discrimination from each other. The present disclosure describes photoluminescent complexes that can enhance the contrast or intensity between two colors and enhance their discrimination from each other.

As used herein, when a compound or chemical structure is referred to as "substituted," it can include one or more substituents. Substituted compounds are derived from an unsubstituted parent structure, wherein one or more hydrogen atoms on the parent structure are independently replaced by one or more substituents. The parent structure may have 1, 2, 3, or more substituents. In some embodiments, the substituent(s) may be independently selected from optionally substituted alkyl, alkenyl, or C ₃ -C ₇ heteroalkyl.

The alkyl moiety can be branched, straight (ie, unbranched), or cyclic. In some embodiments, the alkyl moiety can have 1 to 8 carbon atoms. Alkyl groups of compounds specified herein may be designated as "C ₁ -C ₈ alkyl" or similar designations. By way of example only, "C ₁ -C ₈ alkyl" indicates that 1, 2, 3, 4, 5, 6, 7 or 8 carbon atoms are present in the alkyl chain. That is, the alkyl chain is methyl, ethyl, propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, and any isomer thereof. Therefore, C ₁ -C ₈ alkyl is C ₁ -C ₂ alkyl, C ₁ -C ₃ alkyl, C ₁ -C ₄ alkyl, C ₁ -C ₅ alkyl, C ₁ -C ₆ alkyl, C ₁ -C _{7 alkyl} . Includes alkyl and C ₁ -C ₈ alkyl. Alkyl groups can be substituted or unsubstituted. Typical alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, ethenyl, propenyl, butenyl, cyclopropyl, cyclobutyl, cyclopentyl, Examples include cyclohexyl.

As used herein, the term "heteroalkyl" refers to an alkyl group, as defined herein, in which one or more member carbon atoms have been replaced by a nitrogen, oxygen, or sulfur atom. Point. Examples include, but are not limited to, -CH ₂ -O-CH ₃ , -CH ₂ -CH ₂ -O-CH ₃ , -CH ₂ -NH-CH ₃ , -CH ₂ -N(CH ₃ ) -CH ₃ , -CH ₂ -CH ₂ -NH-CH ₃ , -CH ₂ -CH ₂ -N(CH ₃ )-CH ₃ , -CH ₂ -S-CH ₂ -CH ₃ , -CH ₂ -CH ₂ -S(O) _-CH3 is mentioned. In some embodiments, up to two heteroatoms may be consecutive, such as -CH ₂ -NH-O-CH ₃ .

The term "aromatic" refers to a planar ring having a delocalized π-electron system containing 4n+2 π-electrons, where n is an integer. Aromatic rings may be formed from 5, 6, 7, 8, 9, or 10 or more atoms. Aromatic rings may be optionally substituted. The term "aromatic" includes both carbocyclic aryl (eg, phenyl or naphthylenyl) and heterocyclic aryl (ie, "heteroaryl" or "heteroaromatic") groups (eg, pyridine). The term includes monocyclic groups or fused ring polycyclic (ie, rings sharing adjacent pairs of carbon atoms) groups.

As used herein, the term "aryl" refers to an aromatic ring in which each of the atoms forming the ring is a carbon atom. Aryl rings can be formed by 5, 6, 7, 8, or 9 or more carbon atoms. Aryl groups can be substituted or unsubstituted. Examples of aryl groups include, but are not limited to, phenyl, naphthalenyl, phenanthrenyl, and the like.

The term "aralkyl" refers to an alkyl radical, as defined herein, substituted with aryl, as defined herein. Non-limiting aralkyl groups include benzyl, phenethyl, and the like.

The term "halogen" as used herein refers to fluorine, chlorine, bromine, and iodine.

As used herein, the term "bond," "attached," "direct bond," or "single bond" refers to when the atoms joined by a bond are considered to be part of a larger structure. means a chemical bond between two atoms or between two moieties.

The term "moiety" as used herein refers to a particular segment or functional group of a molecule. A chemical moiety is often understood as a chemical moiety embedded within or added to a molecule.

The term "ester" refers to the formula -COOR, where R is alkyl, cycloalkyl, aryl, heteroaryl (attached via a ring carbon), and heterocycle (attached via a ring carbon). Refers to a chemical moiety that has the following formula: Any hydroxyl or carboxyl moiety of the compounds described herein may be esterified. Any suitable method or procedure may be employed to prepare any ester derivative.

を有する化学的部分を指す。 As used herein, the term "BODIPY" refers to the following formula:

refers to a chemical moiety that has

The BODIPY moiety may be composed of a dipyrromethene structure complexed with a disubstituted boron atom, typically a _BF2 unit. The IUPAC name for the BODIPY core is 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene.

を有する化学的部分、例えば、１Ｈ－キサンテノ［２，１，９－ｄｅｆ］イソキノリン－１，３（２Ｈ）－ジオンを指す。 As used herein, the term "xanthenoisoquinoline" or "xanthenoisoquinoline derivative" or "XI derivative" refers to the formula:

For example, 1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione.

The present disclosure relates to photoluminescent complexes that absorb light energy at a first wavelength and emit light energy at a second, higher wavelength. The photoluminescent complexes of the present disclosure include an absorbing emissive moiety and an emissive emissive moiety connected via a linker, the distance between which is optimized such that the absorbing emissive moiety transfers its energy to the acceptor emissive moiety, The emissive portion then emits energy at a second wavelength that is greater than the absorbed first wavelength.

In some embodiments, the photoluminescent complex includes a blue light absorbing xanthenoisoquinoline derivative (XI derivative), a linker conjugate, and a boron-dipyrromethene (BODIPY) moiety. In some embodiments, the linker complex can covalently attach the xanthenoisoquinoline derivative to the BODIPY moiety. In some embodiments, the xanthenoisoquinoline derivative absorbs light at a first excitation wavelength and transfers energy to the BODIPY moiety, which then emits light energy at a second wavelength; The light energy of the second wavelength is higher than the first (absorbed) wavelength. Energy transfer from the excited xanthenoisoquinoline derivative to the BODIPY moiety is believed to occur via Forster resonance energy transfer (FRET). This idea is due to the absorption/emission spectra of photoluminescent complexes, which have two main absorption bands, one in the blue light absorption band (xanthenoisoquinoline derivatives) and the other in the BODIPY absorption band; There is only one emission band at the emission wavelength of the part (see Figures 1, 2, 3, and 4).

In some embodiments, photoluminescent complexes can have high emission quantum yields. In some examples, the emission quantum yield may exceed 50%, 60%, 70%, 80%, or 90%. In some embodiments, the emission quantum yield is 50%, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or It can exceed 95%. The emission quantum yield can be measured by dividing the number of photons emitted by the number of photons absorbed, which is equal to the emission efficiency of the emissive part. In some embodiments, the absorbing emissive moiety can have an emission quantum yield of greater than 80%. In some embodiments, the quantum yield is 0.8 (80%), 0.81 (81%), 0.82 (82%), 0.83 (83%), 0.84 (84 %), 0.85 (85%), 0.86 (86%), 0.87 (87%), 0.88 (88%), 0.89 (89%), 0.9 (90%) , 0.91 (91%), 0.92 (92%), 0.93 (93%), 0.94 (94%), or 0.95 (95%), up to 1 (100%). Quantum yield measurements on films can be performed by a spectrophotometer, such as a Quantaurus-QY spectrophotometer (Hamamatsu, Inc., Campbell, Calif., USA).

In some embodiments, the photoluminescent complex has an emission band with a full width at half maximum (FWHM) of less than 40 nm. FWHM is the width of the emission band in nanometers at an emission intensity that is half the maximum emission intensity for the band. In some embodiments, the photoluminescent complex has an emission band FWHM value of about 35 nm or less, about 30 nm or less, about 25 nm or less, or about 20 nm or less.

In some embodiments, the photoluminescent complex can have a Stokes shift of 45 nm or greater. As used herein, the term "Stokes shift" means the distance between the excitation peak of the blue light absorbing moiety and the emission peak of the BODIPY moiety.

Photoluminescent complexes of the present disclosure can have tunable emission wavelengths. By incorporating certain substituents on the BODIPY moiety, the emission wavelength can be tuned to a wavelength between about 610 nm and about 645 nm.

In some embodiments, the blue light absorbing moiety may have a peak absorption maximum wavelength between about 400 nm and about 470 nm. In some embodiments, the peak absorption wavelength is about 400 nm to about 405 nm, about 405 nm to 410 nm, about 410 nm to 415 nm, about 415 nm to 420 nm, about 420 nm to 425 nm, about 425 nm to 430 nm, about 430 nm to 435 nm, about between 435 nm and 440 nm, between about 440 nm and 445 nm, between about 445 nm and 450 nm, between about 450 nm and 455 nm, between about 455 nm and 460 nm, between about 460 nm and 465 nm, between about 465 nm and 470 nm, or within a range limited by any of these values. It may be any wavelength.

In some embodiments, the photoluminescent complex is about 610 nm to about 645 nm, about 610 nm to 615 nm, about 615 nm to 620 nm, about 620 nm to 625 nm, about 625 to 630 nm, about 630 nm to 635 nm, about 635 nm to 640 nm, about It can have an emission peak wavelength of 640 nm to 645 nm, or any wavelength within the range limited by either of these values.

The photoluminescent complexes of the present disclosure include a blue light absorbing xanthenoisoquinoline derivative, a linker complex, and a BODIPY moiety. The linker complex covalently links the blue light absorbing xanthenoisoquinoline derivative and the emitting BODIPY moiety. In some embodiments, the xanthenoisoquinoline derivative absorbs light energy at a first excitation wavelength and transfers energy to a BODIPY moiety, and the BODIPY moiety absorbs energy from the xanthenoisoquinoline derivative and transfers energy to a second excitation wavelength. emits light energy at higher wavelengths. In some embodiments, the photoluminescent complex has an emission quantum yield of greater than 80%. In some embodiments, the photoluminescent complex is constructed such that the spatial distance between the blue light absorbing xantenoisoquinoline derivative and the BODIPY moiety is optimized via the linker conjugate. In some examples, the transfer of energy of the blue light absorbing xantenoisoquinoline derivative to the BODIPY moiety can be adjusted to optimize the quantum yield of the photoluminescent complex.

のもの、例えば、１Ｈ－キサンテノ［２，１，９－ｄｅｆ］イソキノリン－１，３（２Ｈ）－ジオンであり得て、式中、Ｒ^０及びＲ^１０は、水素原子（Ｈ）、メチル、又は任意に置換されたアリールから選択することができる。幾つかの実施形態においては、任意に置換されたアリール基は、置換されたフェニル基又はベンジル基であり得る。 Some embodiments include blue light absorbing xanthenoisoquinoline derivatives (XI derivatives), wherein the blue light absorbing xantenoisoquinoline derivatives have the following general formula:

for example, 1H-xanteno[2,1,9-def]isoquinoline-1,3(2H)-dione, where R ⁰ and R ¹⁰ are hydrogen atoms (H), methyl, or optionally substituted aryl. In some embodiments, an optionally substituted aryl group can be a substituted phenyl or benzyl group.

であり得る。 In some embodiments, the optionally substituted aryl group of R ⁰ and/or R ¹⁰ can be substituted with a trifluoromethyl group. In some embodiments, optionally substituted aryl is 3,5-bis(trifluoromethyl)phenyl:

It can be.

であり得る。 In some embodiments, R ⁰ and/or R ¹⁰ optionally substituted aryl is 4-trifluoromethylphenyl:

It can be.

であり得る。 In some embodiments, the optionally substituted aryl of R ⁰ and/or R ¹⁰ is

It can be.

The linker complex covalently attaches the blue-absorbing xanthenoisoquinoline derivative to the BODIPY moiety. In some embodiments, the linker conjugate can be tailored to optimize the spatial distance between the blue light absorbing xanthenoisoquinoline derivative and the BODIPY moiety. By optimizing the spatial distance between the xanthenoisoquinoline derivative and BODIPY, the quantum yield can be optimized. In some embodiments, the distance separating the blue light absorbing xantenoisoquinoline derivative and the BODIPY moiety can be about 8 Å or more.

In some embodiments, the linker complex of the photoluminescent complex covalently attaches a blue light absorbing xanthenoisoquinoline derivative to the BODIPY moiety. In some embodiments, the linker complex can include a single bond between the xanthenoisoquinoline derivative and the BODIPY moiety.

の中から選択することができる。 In some embodiments, the linker conjugate may include an optionally substituted ester group. In some examples, the linker may include an optionally substituted ether group. In some embodiments, the linker conjugate may include both an optionally substituted ester group and an optionally substituted ether group. In some embodiments, the linker conjugate can include an optionally substituted C ₂ -C ₇ ester group. If the linker complex contains a substituted ester group, the linker complex has the following structure:

You can choose from.

のうちの１つである。 In some embodiments, the linker conjugate may include an unsubstituted ester group. When the linker complex contains an unsubstituted ester group, the linker complex has the following structure:

This is one of them.

（式中、ｎは２、３、４又は５である）であり得る。 In some embodiments, the linker conjugate may include an optionally substituted C ₂ -C ₅ ether group. When the linker complex contains an optionally substituted ether group, the linker complex is

(wherein n is 2, 3, 4 or 5).

（式中、ｎは１、２、又は３である）であり得る。 In some embodiments, the linker complex is

(where n is 1, 2, or 3).

（式中、ｎは１、２、又は３である）であり得る。 In some embodiments, the linker complex is

(where n is 1, 2, or 3).

（式中、ｎは１、２、又は３である）であり得る。 In some embodiments, the linker complex is

(where n is 1, 2, or 3).

（式中、ｎは１、２、又は３である）であり得る。 In some embodiments, the linker complex is

(where n is 1, 2, or 3).

（式中、ｎは１、２、又は３である）であり得る。 In some embodiments, the linker complex is

(where n is 1, 2, or 3).

であり得る。 In some embodiments, the linker complex is

It can be.

を有するＢＯＤＩＰＹ誘導体を含む。 Some embodiments have the following general formula:

BODIPY derivatives having the following.

In some embodiments, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are independently a hydrogen atom (H), a C ₁ -C ₃ alkyl group, an optionally substituted selected from aryl groups or ether groups. In some embodiments, R ⁷ , R ⁸ , and R ⁹ can be independently selected from a hydrogen atom (H), a methyl group (-CH ₃ ), or -Cl.

）、ジフェニル基（例えば、

）及び／又はＣ_２～Ｃ_１０アルキルエーテル基を持つジフェニル基（例えば、

）であり得る。 The BODIPY moiety of the present disclosure may be a BODIPY moiety where R ³ and R ⁴ can each be an aryl group, such as a phenyl group. In some embodiments, R ¹ , R ² , R ⁵ and/or R ⁶ are independently a hydrogen atom (H), a substituted aryl group, such as a phenyl group (

), diphenyl group (e.g.

) and/or diphenyl groups with C ₂ -C ₁₀ alkyl ether groups (e.g.

).

又はそれらの組み合わせ。 The photoluminescent complexes of the present disclosure can be represented by the following, which is provided for illustrative purposes and should not be construed as a limitation in any way:

or a combination thereof.

Some embodiments include a color conversion film that includes a color conversion layer that includes a resin matrix and one or more photoluminescent complexes described herein dispersed within the resin matrix.

Some embodiments include color conversion films that can be between about 1 μm and about 200 μm thick. In some embodiments, the color conversion film is about 1 μm to 5 μm, about 5 μm to 10 μm, about 10 μm to 15 μm, about 1 μm to 20 μm, about 20 μm to 40 μm, about 40 μm to 80 μm, about 80 μm to 120 μm, about 120 μm ~160 μm, about 160 μm to 200 μm, or any thickness within the range limited by any of these ranges.

In some embodiments, the color conversion film can absorb light in a wavelength range of about 400 nm to about 480 nm and can emit light in a wavelength range of about 610 nm to about 645 nm.

In some embodiments, the color conversion film may further include a transparent substrate layer. The transparent substrate layer has two opposing surfaces, where the color conversion layer is disposed on the surface of the transparent layer that will be adjacent to the light emitting source and can be in physical contact therewith. The transparent substrate is not particularly limited, and those skilled in the art will be able to select an appropriate transparent substrate. Some non-limiting examples of transparent substrates include PE (polyethylene), PP (polypropylene), PEN (polyethylene naphthalate), PC (polycarbonate), PMA (polymethyl acrylate), PMMA (polymethyl methacrylate). , CAB (cellulose acetate butyrate), PVC (polyvinyl chloride), PET (polyethylene terephthalate), PETG (glycol-modified polyethylene terephthalate), PDMS (polydimethylsiloxane), COC (cycloolefin copolymer), PGA (polyglycolide or polyethylene terephthalate), glycolic acid), PLA (polylactic acid), PCL (polycaprolactone), PEA (polyethylene adipate), PHA (polyhydroxyalkanoate), PHBV (poly(3-hydroxybutyrate-co-3-hydroxyvalerate)), Examples include PBE (polybutylene terephthalate) and PTT (polytrimethylene terephthalate). Either alone or in combination, any of the resins described above can provide the transparent base layer.

In some embodiments, a transparent substrate can have two opposing surfaces. In some embodiments, a color conversion film may be disposed on and in physical contact with one of the opposing surfaces. In some embodiments, the side of the transparent substrate on which the color conversion film is not disposed may be adjacent to the light source. In some examples, the substrate can function as a support during the fabrication of the color conversion film. The type of substrate used is not particularly limited, and the material and/or thickness are not limited as long as it is transparent and can function as a support. Any suitable substrate material and thickness may be employed as the supporting substrate.

Some embodiments include a method of making a color conversion film, the method comprising dissolving a photoluminescent compound described herein and a binder resin in a solvent and applying the mixture to the surface of a transparent substrate. including applying.

Binder resins that can be used with the photoluminescent complex(es) include acrylic resins, polycarbonate resins, ethylene-vinyl alcohol copolymer resins, ethylene-vinyl acetate copolymer resins and their saponification products. , AS resin, polyester resin, vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral resin, polyvinylphosphonic acid (PVPA), polystyrene resin, phenol resin, phenoxy resin, polysulfone, nylon, cellulose resin, and cellulose acetate resin, etc. Examples include resin. In some embodiments, the binder resin can be a polyester resin and/or an acrylic resin.

In some embodiments, solvents that may be used to dissolve or disperse the photoluminescent complex and resin include alkanes such as butane, pentane, hexane, heptane, and octane, cycloalkanes such as cyclopentane, Cyclohexane, cycloheptane, and cyclooctane, alcohols such as ethanol, propanol, butanol, amyl alcohol, hexanol, heptanol, octanol, decanol, undecanol, diacetone alcohol, and furfuryl alcohol, Cellosolves™, such as Methyl Cellosolve (TM), Ethyl Cellosolve(TM), Butyl Cellosolve(TM), Methyl Cellosolve(TM) Acetate, and Ethyl Cellosolve(TM) Acetate, propylene glycol and its derivatives, such as propylene glycol monomethyl ether, propylene glycol monoethyl ether , Propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, and dipropylene glycol dimethyl ether, ketones such as acetone, methyl amyl ketone, cyclohexanone, and acetophenone, ethers such as dioxane and tetrahydrofuran, esters such as butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, diethyl oxalate, ethyl pyruvate, ethyl 2-hydroxybutyrate, ethyl acetoacetate, methyl lactate, ethyl lactate, and methyl 3- methoxypropionate, halogenated hydrocarbons such as chloroform, methylene chloride, and tetrachloroethane, aromatic hydrocarbons such as benzene, toluene, xylene, and cresol, and highly polar solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone.

Some embodiments include a backlight unit that may include the color conversion film described above.

Other embodiments may describe display devices that may include a backlight unit as described herein.

Unless otherwise indicated, all numbers used in this specification and embodiments expressing characteristics such as amounts of components, molecular weights, reaction conditions, etc. are modified in all cases by the term "about." It should be understood that Accordingly, unless indicated to the contrary, the numerical parameters set forth herein and in the accompanying embodiments are approximations that may vary depending on the desired properties sought to be obtained. At least not as an attempt to limit the application of the doctrine of equivalents. Within the scope of the embodiments, each numerical parameter should at least be interpreted in light of the reported number of significant digits and by applying normal rounding techniques.

For the disclosed processes and/or methods, the functions performed in the processes and methods may be implemented in various orders as may be indicated by the context. Further, the steps and operations outlined are provided by way of example only; some steps and operations may be optional, combined into fewer steps and operations, or expanded to additional steps and operations. can be done.

This disclosure may sometimes describe different components included within or connected to different other components. Such depicted configurations are merely exemplary, and many other configurations may be implemented that accomplish the same or similar functionality.

In general, the terms used in this disclosure and the accompanying embodiments (e.g., the text of the accompanying embodiments) are intended as "open" terms (e.g., the term "including" means "limited"). "including, but not limited to" and the term "having" should be interpreted as "having at least." (and the term "includes" should be interpreted as "includes, but not limited to," etc.) Furthermore, when a certain number of elements are introduced, this can be interpreted to mean at least the stated number, as may be indicated by the context (e.g. "two stated numbers" without other modifiers). "The verbatim statement means at least two statements of two or more statements). As used in this disclosure, any disjunctive word and/or phrase expressing two or more alternative terms contemplates the possibility of including one, either, or both of the terms. should be understood as such. For example, the phrase "A or B" will be understood to include the possibilities "A" or "B" or "A and B."

The singular terms ("a", "an", "the") and similar referents used in the context of describing the present disclosure (particularly in the context of the following embodiments) are specifically used herein. Unless otherwise indicated or clearly contradicted by context, both singular and plural terms should be construed to include the singular and plural terms. The use of any and all examples or representative language (e.g., "such as") set forth herein is merely intended to better clarify the disclosure, and any embodiments does not impose any limitations on the scope of. No language in the specification should be construed as indicating any nonspecific element essential to the practice of the disclosure.

Groupings of alternative elements or embodiments disclosed herein are not to be construed as limitations. Each group member may be referred to and embodied individually or in any combination with other members of the group or other elements found herein. It is anticipated that one or more members of a group may be included in or removed from a group for reasons of convenience. If such inclusions or deletions are made, the specification is considered to include the modified group and thus satisfy the description of all Markush groups used in the accompanying embodiments.

Certain embodiments are described herein, including the best mode known to the inventors for carrying out the present disclosure. Of course, variations on these described embodiments will be apparent to those skilled in the art upon reading the above description. The inventors anticipate that those skilled in the art will employ such variations as appropriate, and the inventors anticipate that the disclosure may be practiced otherwise than as specifically described herein. It is intended that Accordingly, embodiments include all modifications and equivalents of the subject matter described in the embodiments as permitted by applicable law. Furthermore, unless indicated otherwise herein or clearly contradicted by context, all combinations of the above-described elements in all possible variations thereof 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, by way of example and not limitation, alternative embodiments may be utilized in accordance with the teachings herein. Therefore, embodiments are not limited to the precise embodiments shown and described.

Embodiment 1. A photoluminescent complex,
a blue light-absorbing xanthenoisoquinoline derivative;
a linker complex that is an unsubstituted ester or a substituted ester;
a boron-dipyrromethene (BODIPY) moiety;
including;
A linker complex covalently bonds the xanthenoisoquinoline derivative and the BODIPY moiety, the xanthenoisoquinoline derivative absorbs light energy at the first excitation wavelength and transfers energy to the BODIPY moiety, and the BODIPY moiety A photoluminescent complex that absorbs energy from a derivative and emits light energy at a second, higher wavelength, wherein the photoluminescent complex has an emission quantum yield of greater than 80%.

（式中、Ｒ^０は、結合、Ｈ、Ｃ_１～Ｃ_３メチル基、又は任意に置換されたアリール基である）のものである、実施形態１のフォトルミネッセンス錯体。 2. Xanthenoisoquinoline derivatives have the general formula:
3.

The photoluminescent complex of embodiment 1, wherein R ⁰ is a bond, H, a C ₁ -C ₃ methyl group, or an optionally substituted aryl group.

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６は、独立して、結合、Ｈ、Ｃ_１～Ｃ_３アルキル、アリール及び／又はエーテルから選択され、
Ｒ^７、Ｒ^８、及びＲ^９は、独立して、結合、Ｈ、又はメチル基（－ＣＨ_３）から選択することができる）のものである、実施形態１のフォトルミネッセンス錯体。 4. The BODIPY part is a general formula:

(wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ are independently selected from a bond, H, C ₁ -C ₃ alkyl, aryl and/or ether;
The photoluminescent complex of embodiment 1, wherein R ⁷ , R ⁸ , and R ⁹ can be independently selected from a bond, H, or a methyl group (-CH ₃ ).

5. R ³ and R ⁴ can each be an aryl group, for example a phenyl group,
Photoluminescent complex of embodiment 4.

6. The photoluminescent complex of embodiment 5, wherein the aryl group can be a phenyl group.

）、又はジフェニル基（

）であり得る、実施形態４のフォトルミネッセンス錯体。 7. The substituted aryl group is a phenyl group (

), or diphenyl group (

) The photoluminescent complex of embodiment 4, which may be ).

）であり得る、実施形態４のフォトルミネッセンス錯体。 8. The ether group is a C2-C10 alkyl ether group (

) The photoluminescent complex of embodiment 4, which may be ).

から選択され得る、実施形態１のフォトルミネッセンス錯体。 9. The linker is

The photoluminescent complex of embodiment 1, which may be selected from.

である、実施形態１のフォトルミネッセンス錯体。 10. The unsubstituted ester linker is

The photoluminescent complex of Embodiment 1, which is.

のうちの１つである、実施形態１、２、３、４、５、６、７、８、９、１０、及び１１のフォトルミネッセンス錯体。 11. The substituted ester of the linker complex has the following structure:

The photoluminescent complex of embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and 11.

又はそれらの組み合わせ
のうちの１つである、実施形態１のフォトルミネッセンス錯体。 12. The photoluminescent complex has the following structure:

or one of a combination thereof, the photoluminescent complex of embodiment 1.

13. A color conversion film,
a transparent base material layer;
a color conversion layer including a resin matrix;
The photoluminescent complex of embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, and 12, wherein the photoluminescent compound is dispersed within the resin matrix. at least one photoluminescent complex comprising a luminescent compound;
Including color conversion film.

14. The color conversion film of embodiment 13, further comprising a singlet oxygen quencher.

15. The color conversion film of embodiment 13 further comprising a free radical scavenger.

16. The color conversion film of embodiment 13, wherein the film has a thickness between 10 μm and 200 μm.

17. The color conversion film of embodiment 13, wherein the film absorbs light in a wavelength range of about 400 nm to about 480 nm and emits light in a wavelength range of 575 nm to about 645 nm.

18. A method of producing a color conversion film, the method comprising:
Dissolving the photoluminescent complex of embodiment 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 and the binder resin in a solvent;
applying the mixture to one of the opposing surfaces of the transparent substrate;
including methods.

19. A backlight unit including the color conversion film of Embodiment 13.

20. A display device including the backlight unit of embodiment 19.

It has been discovered that the photoluminescent complex embodiments described herein have improved performance compared to other forms of dyes used in color conversion films. These advantages are further illustrated by the following examples, which are for the purpose of illustrating the disclosure only and are in no way intended to limit the scope or underlying principles.

Example 1.1 Comparative Example 1 (CE-1):

CE-1: 0.75 g of 4-hydroxyl-2,6-dimethylbenzaldehyde (5 mmol) and 1.04 g of 2,4-dimethylpyrrole (11 mmol) were dissolved in 100 mL of anhydrous dichloromethane. The solution was degassed for 30 minutes. Next, 1 drop of trifluoroacetic acid was added. The solution was stirred at room temperature overnight under an atmosphere of argon gas. DDQ (2,3-dichloro-5,6-dicyano-1,4-benzoquinone) (2.0 g) was added to the resulting solution, and the mixture was stirred overnight. The next day, the solution was filtered and washed with dichloromethane to obtain dipyrolemethane (1.9 g). Next, 1.0 g of dipyrolemethane was dissolved in 60 mL of THF. After adding 5 mL of trimethylamine to the solution, it was degassed for 10 minutes. After degassing, 5 mL of trifluoroboron-diethyl ether was added slowly followed by heating at 70° C. for 30 minutes. The resulting solution was loaded onto silica gel and purified by flash chromatography using dichloromethane as eluent. The desired fractions were collected and dried under reduced pressure to yield 0.9 g of an orange solid (76% yield). LCMS ( _APCI +): Calculated _{for C21H24BF2N2O (} M+H) = 369; Found: 369. 1H NMR (400MHz, chloroform-d) δ 6.64 (s, 2H), 5. 97 (s, 2H), 4.73 (s, 1H), 2.56 (s, 6H), 2.09 (s, 6H), 1.43 (s, 6H).

Example 1.2 Comparative Example 2 (CE-2) was synthesized as described in Wakamiya, Atsushi et al. Chemistry Letters, 37(10), 1094-1095; 2008.

Example 2: Synthesis of photoluminescent complex:
Synthesis of compound PLC-1:

Compound 1-(4-bromophenyl)-4-nitro-3-phenylbutan-1-one (PLC-1.1):
The compound 1-(4-bromophenyl)ethane-1-one (70% .1g, 352mmol, 1.50eq) was added and stirred at -78°C for 30 minutes. Compound (E)-(2-nitrovinyl)benzene (35.0 g, 235 mmol, 1.00 equivalent) was added to this mixture, and the mixture was stirred at -78°C for 1 hour. Thin layer chromatography (TLC) (petroleum ether: ethyl acetate = 5:1) showed that compound (E)-(2-nitrovinyl)benzene was consumed and a new spot was formed. The reaction mixture was quenched by adding 200 mL of aqueous NH _Cl at −70 °C, extracted with 600 mL of ethyl acetate (EtOAc) (200 mL x ₃ ), dried over Na ₂ SO , filtered, and concentrated under reduced pressure. , a residue was obtained. The residue was purified by column chromatography (SiO ₂ , petroleum ether/ethyl acetate = 1/0→5/1). Compound 1-(4-bromophenyl)-4-nitro-3-phenylbutan-1-one (PLC-1.1) (40.0 g, 115 mmol, 48.9% yield) was obtained as a white solid. This was confirmed by ¹ HNMR. ¹ HNMR: (400MHz, MeOD): δ 7.95-7.78 (m, 2H), 7.70-7.63 (m, 2H), 7.38-7.28 (m, 4H), 7 .28-7.19 (m, 1H), 4.97-4.88 (m, 1H), 4.83-4.74 (m, 1H), 4.22-4.10 (m, 1H) , 3.51 (dq, J=7.0, 17.5Hz, 2H).

Compound 2-(4-bromophenyl)-4-phenyl-1H-pyrrole (PLC-1.2): Compound 1-(4-bromophenyl)-4-nitro-3-phenylbutan-1-one (PLC- 1.1) (40.0 g, 115 mmol, 1.00 eq), sulfur (11.1 g, 345 mmol, 3.00 eq), _NH4OAc (53.1 g, 689 mmol, 6.00 eq) and morpholine (30 .0 g, 345 mmol, 30.3 mL, 3.00 eq.) was stirred at 80° C. for 1 hour. TLC (petroleum ether/ethyl acetate = 5/1) shows that the compound 1-(4-bromophenyl)-4-nitro-3-phenylbutan-1-one (PLC-1.1) is consumed and a new spot was formed. The reaction mixture was quenched with H ₂ O (200 mL) at 15° C. and extracted with 600 mL of EtOAc (200 mL×3). The combined organic layers were concentrated under reduced pressure to obtain a residue. The residue was purified by column chromatography (SiO ₂ , petroleum ether/ethyl acetate = 1/0→5/1) and further purified by washing with MTBE (methyl tert-butyl ether) (100 mL). Compound 2-(4-bromophenyl)-4-phenyl-1H-pyrrole (PLC-1.2) (10.6 g, 35.2 mmol, 30.6% yield, 99% purity) was obtained as a blue solid. This was confirmed by ¹ HNMR. ¹ HNMR: (400MHz, DMSO-d6): δ 11.5 (br d, J=0.9Hz, 1H), 7.64-7.56 (m, 4H), 7.56-7.51 (m , 2H), 7.35 (dd, J = 1.8, 2.6Hz, 1H), 7.30 (t, J = 7.8Hz, 2H), 7.15 to 7.07 (m, 1H) , 6.99 (t, J=2.0Hz, 1H).

Compound PLC-1.3: Step-1: 2-(4-bromophenyl)-4-phenyl-1H-pyrrole (PLC-1.2) (1.0 g, 3 A mixture of 2,4,6-trimethylbenzaldehyde (0.249 g, 1.68 mmol) and tosylic acid (50 mg) was heated at 50° C. for 24 hours. LCMS analysis shows the main peak is the desired product with m/e+=727.

Step-2: DDQ (2,3-dichloro-5,6-dicyano-1,4-benzoquinone) (454 mg, 2 mmol) was added to the mixture from Step-1 and stirred at room temperature for 1 hour. LCMS analysis shows that the reaction is complete with one main peak at m/e-=724.

Step-3: Triethylamine (0.85 mL, 6 mmol) and boron trifluoride diethyl etherate (BF ₃ .OEt ₂ ) (1.1 mL, 9 mmol) were added to the mixture from step-2 at 0°C. The whole was heated at 50°C for 1 hour. Another portion of triethylamine (0.5 mL) and BF ₃ .OEt ₂ (0.5 mL) were added and the mixture was heated at 50° C. for an additional 1 h. LCMS shows the reaction is complete with a main peak at m/e ⁻ =772. The mixture was diluted with 50 mL dichloromethane (DCM), then washed twice with water and once with brine, then concentrated to 100 mL, loaded onto silica gel, and eluted with hexane/DCM (40% → 100% DCM). Purified using flash chromatography. After collecting the desired main peak and removing the solvent under reduced pressure, the desired product was obtained as a purple solid (1.06 g, 81.6% yield). Confirmed by LCMS (APCI): Calcd for C ₄₂ H ₃₁ BBr ₂ F ₂ N ₂ (M-): 770.1; Found: 770. ^1H NMR (400MHz, chloroform-d) δ 7.81-7.73 (m, 4H), 7.61-7.53 (m, 4H), 6.99-6.90 (m, 2H), 6.85 (dd, J=8.3, 6.9Hz, 4H), 6.78 to 6.71 (m, 4H), 6.42 (s, 2H), 6.00 (s, 2H), 1.98 (s, 6H), 1.85 (s, 3H).

Compound PLC-1.4: Compound PLC-1.3 (160 mg, 0.207 mmol) in 1,4-dioxane/water (8 mL/1 mL), 4-(4,4,5,5-tetramethyl-1) , 3,2-dioxaborolan-2-yl)phenol (120mg, 0.54mmol), tetrakis(triphenylphosphine)palladium(0)(Pd(PPh ₃ ) ₄ ) (25mg, 0.022mol), potassium carbonate (140mg , 1.01 mmol) was degassed and then heated at 120° C. for 90 minutes in a microwave reactor. The resulting mixture was diluted with 20 mL of DCM, loaded onto silica gel, and purified by flash chromatography using an eluent of DCM/ethyl acetate (0%→20% ethyl acetate). After collecting the desired main peak and removing the solvent under reduced pressure, the desired product was obtained as a dark solid (130 mg, 79% yield). ^1H NMR (400MHz, TCE-d2) δ 7.98-7.91 (m, 4H), 7.62-7.54 (m, 4H), 7.54-7.46 (m, 4H), 6.92-6.85 (m, 4H), 6.84 (d, J=2.1Hz, 2H), 6.82-6.74 (m, 4H), 6.73-6.66 (m , 4H), 6.46 (s, 2H), 5.92 (s, 2H), 4.88 (s, 2H), 1.92 (s, 6H), 1.78 (s, 3H).

Compound PLC-1.5: A mixture of 2-nitrophenol (6.6 g, 48 mmol), KOH powder (2.4 g, 43 mmol) was mixed and stirred under vacuum for 30 minutes, then copper powder (0.4 g) was added followed by 100 mL of anhydrous dimethylformamide (DMF). The mixture was stirred for 5 minutes and then 4-chloronaphthalic anhydride (5.1 g, 22 mmol) was added. The whole was degassed and then 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, which was left to stand for 2 hours. The precipitate was collected by filtration and then dried under vacuum overnight to give a tan solid (4.6 g). This was further purified by stirring in refluxing acetic acid (50 mL) for 2 hours, then cooling to room temperature. Filtration and drying in air gave a yellow solid (3.0 g, 41% yield). Confirmed _by LCMS (APCI): Calcd for _C18H10NO6 (M+H): 336.0; Found: ₃₃₆ . ¹ H NMR (400 MHz, chloroform-d) δ 8.80 (dd, J = 8.5, 1.2 Hz, 1H), 8.72 (dd, J = 7.3, 1.2 Hz, 1H), 8 .50 (d, J=8.2Hz, 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, 1.7 Hz, 1H), 7.54 (td, J = 8.0, 1.3 Hz, 1H), 7.39 (dd, J = 8. 3, 1.2Hz, 1H), 6.89 (d, J=8.2Hz, 1H).

Compound PLC-1.6: 4-(2-nitrophenoxyl)-1,8-naphthalic anhydride (2.0 g, 6 mmol) and iron powder (less than 10 μm, 0.91 g, 16 mmol) in acetic acid (75 mL) ) was heated to reflux for 30 minutes. The resulting solution was poured into water (220 mL). The resulting precipitate was collected by filtration, washed with water, thoroughly dried in air, and then dried under vacuum to yield a yellow solid (1.65 g, 90% yield). Confirmed _by LCMS (APCI): Calcd for _C18H12NO4 (M+H): 306.1; _Found : 306.

Compound PLC-1.7: 4-(2-aminophenoxy)-1,8-naphthalic anhydride (PLC-1.6) (1.5 g, 4.9 mmol) was dispersed in acetic acid (35 mL), Cooled to 0°C. While stirring, pre-chilled hydrochloric acid (3 mL, 37 mmol) was added, followed by dropwise addition of a solution of sodium nitrite (3.29 g, 46 mmol) in 12 mL of water at 0<0>C. The whole was stirred at 0° C. for 1 hour, then transferred to an additional funnel and added dropwise to refluxing 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, ethyl acetate, and then dried in air and vacuum to give a yellow solid (0.92 g, 65% yield). Confirmed by LCMS (APCI): Calcd for C ₁₈ H ₈ O ₄ (M-): 288.0; Found: 288. ¹ H NMR (400 MHz, chloroform-d) δ 8.61 (dd, J = 17.1, 8.1 Hz, 2H), 8.09 (d, J = 8.0 Hz, 1H), 7.97 (d , J=7.9Hz, 1H), 7.59 (t, J=7.7Hz, 1H), 7.40 (t, J=8.1Hz, 2H), 7.33 (d, J=8. 4Hz, 1H).

Compound PLC-1.8: 1H,3H-isochromeno[6,5,4-mna]xanthene-1,3-dione (PLC-1.7) (100 mg, 0.347 mmol) in 5 mL of DMF, 4- A mixture of (4-aminophenyl)butanoic acid (125 mg, 0.7 mmol) was heated in a microwave reactor at 165° C. for 2.5 hours. To this mixture, 15 mL of acetone was added and the resulting precipitate was collected by filtration and dried in air to yield a yellow solid (PLC-1.8) (120 mg, 77% yield). . Confirmed _by LCMS (APCI): Calcd for _{C28H19NO5 (} M-): 449.1; Found: 449. ^1H NMR (400MHz, DMSO-d6) δ 8.38 (d, J=41.6Hz, 4H), 7.81-6.97 (m, 8H), 2.69-2.64 (m, 2H ), 2.26 (t, J = 7.2 Hz, 2H), 1.87 (p, J = 7.2 Hz, 2H).

Compound PLC-1: Compound PLC-1.4 (80 mg, 0.1 mmol), Compound PLC-1.8 (100 mg, 0.222 mmol), 4-dimethylaminopyridinium/p-toluenesulfonate (DMAP) in 6 mL of DCM. /TsOH salt) (59 mg, 0.2 mmol), N,N'-diisopropylcarbodiimide (DIC) (0.15 mL) was stirred at room temperature overnight and then at 45° C. for 2 hours. The resulting mixture was loaded onto silica gel and purified by flash chromatography using an eluent of dichloromethane (DCM)/ethyl acetate (0%→10% ethyl acetate). The desired di-coupled product was collected as the second major peak. After removing the solvent, washing with methanol and drying in air, the desired product was obtained as a dark solid (25 mg, 15% yield). Confirmed by HNMR. ^1H NMR (400MHz, TCE-d2) δ 8.49 (dd, J=16.0, 8.1Hz, 4H), 7.99 (d, J=8.2Hz, 6H), 7.85 (d , J=8.0Hz, 2H), 7.63 (dd, J=8.5, 3.7Hz, 8H), 7.50 (t, J=7.8Hz, 2H), 7.42 to 7. 25 (m, 8H), 7.25 to 7.08 (m, 10H), 6.84 (dt, J = 36.5, 7.3Hz, 6H), 6.70 (d, J = 7.5Hz , 4H), 6.48 (s, 2H), 5.93 (s, 2H), 2.80 (t, J = 7.7Hz, 4H), 2.63 (t, J = 7.4Hz, 4H ), 2.11 (t, J=7.7Hz, 4H), 1.92 (s, 6H), 1.78 (s, 3H).

Synthesis of compound PLC-2

Compound PLC-2.1: (4',4'''-(5,5-difluoro-10-mesityl-1,9-diphenyl-5H-4l4,5l4-dipyrrolo[1,2-c:2', 1'-f][1,3,2]diazaborinine-3,7-diyl)bis([1,1'-biphenyl]-3-ol)): in a 30 mL wide-neck microwave vial (Anton-Parr). , stirring bar, compound PLC-1.3 (0.300 mmol, 232 mg), 3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol (0.800 mmol, 177 mg), K ₂ CO ₃ (1.60 mmol, 221 mg), and Pd(PPh ₃ ) ₄ (0.030 mmol, 34.7 mg). Dioxane (8 mL) and water (1 mL) were added to the vial. The vial was sealed with a septum and sparged with argon while stirring for 5 minutes at room temperature. The septum was changed to a snap cap and a septum, and the sample was irradiated for 90 minutes at a target temperature of 120° C. in a microwave synthesizer. The crude reaction mixture was evaporated to dryness, dissolved in a small amount of DCM and loaded onto approximately 60 mL of silica in a solids loader. Purified by flash chromatography on silica gel (120 g, solid, elution with equilibrated 100% hexanes, 100% hexanes (2 CV), 60% EtOAc/hexanes (30 CV)). Fractions containing the product were evaporated to dryness in vacuo to give a dark red solid, 173 mg (72% yield). ¹ H NMR (400 MHz, tetrachloroethane-d2) δ 8.05 (d, J = 8.5 Hz, 4H), 7.70 (d, J = 8.5 Hz, 4H), 7.35 (t, J = 7.8Hz, 2H), 7.27 (dt, J=7.9, 1.2Hz, 2H), 7.15 (dd, J=2.5, 1.6Hz, 2H), 7.00-6 .93 (m, 2H), 6.91-6.83 (m, 6H), 6.82-6.76 (m, 4H), 6.56 (s, 2H), 6.02 (s, 2H) ), 4.94 (s, 2H), 2.00 (s, 6H), 1.87 (s, 3H). MS (APCI): Calculated for formula C ₅₄ H ₄₁ BF ₂ N ₂ O ₂ (M-) = 798; Found: 798.

Compound PLC-2: ((5,5-difluoro-10-mesityl-1,9-diphenyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3, 2] Diazaborinine-3,7-diyl)bis([1,1'-biphenyl]-4',3-diyl)bis(4-(4-(1,3-dioxo-1H-xantheno[2,1, 9-def]isoquinolin-2(3H)-yl)phenyl)butanoate): In a 40 mL screw cap vial, stir bar, compound PLC-2.1 (0.015 mmol, 12.0 mg), 4-(4- (1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)butanoic acid (PLC-1.8) (0.0375 mmol, 16.8 mg), and DMAP·pTsOH salt (0.0075 mmol, 2.2 mg) was added. The vial was sealed with a screw cap under air and placed in a preheated aluminum heat block set at 70°C. After stirring the reaction mixture at 70° C. for several minutes, N,N′-diisopropylcarbodiimide (DIC) (0.060 mmol, 0.0094 mL) was added. The vial was sealed with a screw cap and stirred at 70° C. for 28 hours, then at room temperature for the remainder of the weekend. TLC shows the reaction is not complete. Reheat the vial to 70°C and add additional 4-(4-(1,3-dioxo-1H-xanteno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)butanoic acid (PLC- 1.8) (0.0221 mmol, 9.9 mg) and N,N'-diisopropylcarbodiimide (DIC) (0.060 mmol, 0.0094 mL), followed by 4 mL of anhydrous THF (solubility of all reaction components ) was added to improve the The reaction mixture was stirred at 70° C. for 90 minutes, at which point TLC showed completion of the reaction. The solvent was evaporated to dryness in vacuo, dissolved in a small amount of toluene and loaded onto about 10 g of silica gel with a solid loader. Purified by flash chromatography on silica gel (80 g, solid, elution with equilibrated 100% toluene, 100% toluene (2 CV), then 20% EtOAc/toluene (30 CV)). Removal of the solvent gave 22.0 mg of a red solid (88% yield). ¹ H NMR (400 MHz, chloroform-d) δ 8.59 (dd, J = 13.1, 8.1 Hz, 4H), 8.08-7.99 (m, 6H), 7.89 (d, J =8.0Hz, 2H), 7.68 (d, J = 8.5Hz, 4H), 7.57 to 7.49 (m, 4H), 7.49 to 7.31 (m, 12H), 7 .30 to 7.22 (m, 6H), 7.09 (ddd, J=8.0, 2.4, 1.1Hz, 2H), 6.98 to 6.91 (m, 2H), 6. 86 (t, J=7.6Hz, 4H), 6.81 to 6.75 (m, 4H), 6.51 (s, 2H), 6.01 (s, 2H), 2.85 (t, J=7.6Hz, 4H), 2.68 (t, J=7.4Hz, 4H), 2.17 (p, J=7.6Hz, 4H), 2.02 (s, 6H), 1. 86 (s, 3H).

Compound PLC-3:

Compound PLC-3.1 (Ethyl (2-(4'-(octyloxy)-[1,1'-biphenyl]-4-yl)-4-phenyl-1H-pyrrole-3-carboxylate): All The ground glass joints were secured with Teflon tape. 250 mL of 2N RBF was placed in an aluminum heat block and preheated to 90°C. The flask was fitted with an air condenser with a septum on top, a second A glass stopper was attached to the mouth and a stir bar was placed. The flask was flushed with argon via a needle through the top of an air condenser and then charged with zinc ((granules, 10-20 mesh), 80.0 mmol, 5.231 g). Anhydrous THF (20 mL) was added to the flask, followed by methanesulfonic acid (0.500 mmol, 0.0325 mL). The reaction mixture was stirred at 90 °C for 5 minutes, then 4'-(octyloxy )-[1,1'-biphenyl]-4-carbonitrile (15.0 mmol, 4.611 g) was added.A syringe pump was installed, and benzyl 2-bromoacetate (22.5 mmol, 3.56 mL) was added to the It was added dropwise over 1 h with stirring at °C. The reaction mixture was heated at 90 °C for 20 h. An additional portion of anhydrous THF (10 mL) was added (to replace solvent lost by evaporation) and the reaction The temperature was lowered to 85° C. Beta-nitrostyrene (10.0 mmol, 1.491 g) was added followed immediately by iron trichloride (FeCl ₃ ) (6.00 mmol, 973 mg) and the reaction mixture was heated under argon. Heated at 85° C. for 1 h. The reaction mixture was complete as checked by TLC. The reaction was removed from heat and diluted with ethyl acetate (200 mL) and water (100 mL), then treated with 6N HCl/aqueous solution (20 mL). ) and brine (50 mL) was added to break the emulsion. The layers were separated. Attempting to wash the organic layer with water (100 mL) resulted in another emulsion. The emulsion was washed as before. Disrupted by addition of 6N HCl and brine. The organic layer was dried over _MgSO4 , filtered and evaporated to dryness in vacuo.The crude product was evaporated onto 10:1 Celite:Flash _SiO2 and subjected to silica gel flash chromatography. (330 g, solid, elution with equilibrated 10% DCM/hexanes, 10% DCM/hexanes (2 CV), 100% DCM (20 CV)). Fractions containing the product were evaporated to dryness in vacuo and 1.409 g of an off-white solid was obtained with a yield of 25%. ¹ H NMR (400 MHz, tetrachloroethane-d2) δ 8.52 (d, J = 2.5 Hz, 1H), 7.57 (d, J = 7.4 Hz, 6H), 7.48-7.43 ( m, 2H), 7.39 to 7.28 (m, 3H), 7.26 to 7.17 (m, 3H), 7.02 (d, J = 8.8Hz, 2H), 6.95 to 6.90 (m, 2H), 6.87 (d, J=2.6Hz, 1H), 5.10 (s, 2H), 4.02 (t, J=6.6Hz, 2H), 1. 82 (p, J = 6.8Hz, 2H), 1.54-1.43 (m, 2H), 1.43-1.25 (m, 8H), 0.95-0.88 (m, 3H) ). MS (APCI): Calculated for formula _C33H37NO3 ( _M +H) = ₄₉₆ ; Found: 496.

Compound PLC-3.2: (2-hydroxyethyl 2-(4'-(octyloxy)-[1,1'-biphenyl]-4-yl)-4-phenyl-1H-pyrrole-3-carboxylate) : A 100 mL two-necked round-bottomed flask was placed in an aluminum heat block, fitted with a finned condenser, and equipped with a stirrer. The heat block was preheated to 120°C. To the flask were added compound PLC-3.1 (0.479 mmol, 267 mg) and sodium hydride (NaH) (9.575 mmol, 230 mg, 60% in mineral oil, 383 mg). The second port was fitted with a septum and needle to relieve pressure. Anhydrous ethylene glycol was carefully added to the flask at 120°C with stirring and hydrogen gas was allowed to escape. Once all the hydrogen gas was exhausted, the septum was removed and replaced with a glass stopper. The reaction temperature was increased to 150°C and the reaction mixture was stirred at this temperature for 1 hour. Since the reaction was proceeding slowly (monitored by LCMS), the stirring speed was increased to overcome the insolubility of the starting material in ethylene glycol. The reaction was heated at 150° C. for 3 hours with very vigorous stirring and then at room temperature overnight. The reaction was completed in the morning. The reaction mixture was diluted with water (100 mL) and acidified with 6N HCl/aq (10 mL). After stirring for 1 hour at room temperature, the precipitate was filtered off and washed with water. The crude precipitate was dissolved in ethyl acetate and DCM and evaporated to dryness. The crude product was evaporated in vacuo on flash silica gel and chromatographed on silica gel (120 g, equilibrated with 100% hexane, solids, 100% hexane (2 CV), 5% EtOAc/hexane (0 CV) → 100% EtOAc ( Purified by elution with 30 CV). Fractions containing the product were collected and evaporated to dryness in vacuo to give 127 mg of an off-white solid in 51% yield. ^1H NMR (400MHz, tetrachloroethane-d2) δ 8.54 (d, J = 2.4Hz, 1H), 7.66 (s, 4H), 7.59 (d, J = 8.7Hz, 2H) , 7.50-7.45 (m, 2H), 7.44-7.39 (m, 2H), 7.38-7.32 (m, 1H), 7.01 (d, J=8. 8Hz, 2H), 6.87 (d, J = 2.5Hz, 1H), 4.12 to 4.06 (m, 2H), 4.01 (t, J = 6.6Hz, 2H), 3. 55-3.47 (m, 2H), 1.81 (p, J = 6.7Hz, 2H), 1.53-1.42 (m, 2H), 1.42-1.27 (m, 8H) ), 0.97-0.86 (m, 3H). MS (APCI): Calculated for formula _C33H37NO4 ( _M +H) = ₅₁₂ ; Found: 512.

Compound PLC-3.3: (bis(2-hydroxyethyl)5,5-difluoro-10-mesityl-3,7-bis(4'-(octyloxy)-[1,1'-biphenyl]-4- (PLC -3.3): A stir bar, compound PLC-3.2 (0.244 mmol, 125 mg), and mesitaldehyde (0.1283 mmol, 0.00189 mL) were added to a 40 mL screw capped vial. The headspace was purged with argon, then the vial was sealed with a screw cap septum and placed in an aluminum heat block preheated to 75°C. Anhydrous DCE (5 mL) was added to the vial and the solution was sparged with nitrogen while stirring for 10 minutes at 75° C., then pTsOH (0.0.0366 mmol, 7.0 mg) was added along with anhydrous DCE (3 mL). Nitrogen sparging was continued for an additional 10 minutes at 75°C. The gas was switched to static argon and the reaction mixture was stirred at 75° C. under argon overnight. The next morning, additional mesitaldehyde (0.0339 mmol, 5.03 mg) was added and the reaction mixture was stirred at 75° C. under argon for an additional 30 minutes, at which point TLC showed no starting material. The reaction was removed from the heat, DDQ (2,3-dichloro-5,6-dicyano-1,4-benzoquinone) (0.1586 mmol, 36 mg) was added, and the reaction mixture was stirred at room temperature for 1 min before being placed in a heat block. The oxidation was completed by stirring at 75° C. for 30 minutes. The reaction mixture was cooled to 0° C. and boron trifluoride diethyl etherate (BF ₃ .OEt ₂ ) (1.098 mmol, 0.136 mL) and triethylamine (0.732 mmol, 0.102 mL) were added rapidly and continuously with stirring. and added. The reaction mixture was stirred at 0° C. for 1 min before repeating the addition of BF ₃ .OEt ₂ (1.098 mmol, 0.136 mL) and triethylamine (0.732 mmol, 0.102 mL). After stirring for an additional minute at 0°C, the reaction was returned to the heat block and stirred at 75°C for 2 hours. Additional BF ₃ .OEt ₂ (1.464 mmol, 0.181 mL) and triethylamine (0.732 mmol, 0.102 mL) were added at 75° C. and stirring continued for 45 minutes, at which point all of the dipyrromethene had been removed by TLC. Consumed. Flash silica gel (40 mL) was added to the Erlenmeyer flask and the reaction mixture was diluted into the flask with DCM (approximately 100 mL). Methanol (25 mL) was added to quench the reaction. The reaction mixture was evaporated to dryness onto silica gel in vacuo. The crude reaction was purified by silica gel flash chromatography (80 g, solids, equilibrated with 100% hexane, eluting with 100% hexane (2 CV), 26% EtOAc/hexane (19.7 CV), 100% EtOAc (15 CV)). did. Fractions containing the product were evaporated to dryness in vacuo to give 35 mg of a reddish blue solid in 24% yield. MS (APCI): Calculated value (M-) for formula C ₇₆ H ₈₁ BF ₂ N ₂ O ₈ = 1199; Found value: 1199.

Compound PLC-3 (bis(2-((4-(4-(1,3-dioxo-3,6-dihydroanthra[2,1,9-def]isoquinolin-2(1H)-yl)phenyl)butanoyl )oxy)ethyl)5,5-difluoro-10-mesityl-3,7-bis(4'-(octyloxy)-[1,1'-biphenyl]-4-yl)-1,9-diphenyl-5H -4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylate): 40 mL screw cap vial in aluminum heat block , and a stirring bar was added. PLC-3.3 (0.0146 mmol, 17.5 mg) and 4-(4-(1,3-dioxo-1H-xanteno[2,1,9-def]isoquinolin-2(3H)-yl) in a vial. Phenyl)butanoic acid (0.0438 mmol, 19.6 mg) (PLC-1.8) and DMAP·pTsOH salt (0.0073 mmol, 2.1 mg) were added. Anhydrous DCM (4 mL) was added to the vial. The vial was sealed with a PTFE-lined screw cap and sonicated for approximately 30 seconds. While stirring at room temperature, N,N'-diisopropylcarbodiimide (DIC) (0.073 mmol, 0.0114 mL) was added. The sealed vial was stirred under air at room temperature for 5 minutes, then the heat block was set at 45° C. and the reaction mixture was stirred at this temperature overnight. In the morning, DCM was evaporated under a stream of nitrogen and the solvent was replaced with anhydrous dichloroethane (DCE) (4 mL). The heat block temperature was increased to 70° C. and the reaction mixture was stirred at this temperature for 1 hour to complete the reaction. The crude reaction mixture was loaded onto a cartridge packed with 60 mL of flash silica gel and purified by silica gel flash chromatography (80 g, equilibrated with 100% hexane, eluting with 100% hexane (2 CV), 70% EtOAc/hexane (40 CV)). did. Fractions containing the product were evaporated to dryness in vacuo to give 15.3 mg of a dark solid (57.3% yield). ¹ H NMR (400 MHz, chloroform-d) δ 8.61 (dd, J = 16.2, 8.1 Hz, 4H), 8.07 (dd, J = 8.1, 1.5 Hz, 2H), 7 .94 (d, J=8.0Hz, 2H), 7.68 (d, J=8.1Hz, 4H), 7.60-7.50 (m, 10H), 7.40-7.33 ( m, 4H), 7.29 (d, J=8.3Hz, 6H), 7.21 (d, J=8.3Hz, 4H), 6.97 to 6.88 (m, 6H), 6. 86-6.76 (m, 8H), 5.95 (s, 2H), 3.96 (t, J=6.6Hz, 4H), 3.94-3.88 (m, 4H), 3. 64-3.58 (m, 4H), 2.63 (t, J = 7.6Hz, 4H), 2.20 (t, J = 7.4Hz, 4H), 2.00 (s, 6H), 1.88 (p, J = 7.6Hz, 4H), 1.82 (s, 3H), 1.80 to 1.73 (m, 4H), 1.45 (p, J = 6.7Hz, 4H ), 1.38-1.19 (m, 16H), 0.92-0.84 (m, 6H).

Synthesis of compound PLC-4:

Compound PLC-4.1: To a mixture of PLC-1.7 (290 mg, 1.0 mmol) in ortho-dichlorobenzene (30 mL) was added bromine (1.98 g, 12 mmol). The mixture was heated at 75°C for 30 hours. After cooling to room temperature, the solid was collected by filtration and dried in air to yield 290 mg of a yellow solid as the desired product. The filtrate was loaded onto silica gel and purified by flash chromatography using an eluent of hexane/dichloromethane (50%→100% dichloromethane). The desired fractions were collected and the solvent was removed to yield 110 mg of a yellow solid. A total of 400 mg of product was obtained with a yield of 89.7%. LCMS _{( APCI-} ): Calcd for _C18H6Br2O4 ( _M- ): 443.9; Found: 444. ^1H NMR (400MHz, d2-TCE) δ 9.40 (dd, J=8.5, 1.5Hz, 1H), 8.71 (s, 1H), 8.67 (s, 1H), 7. 60 (ddd, J=8.4, 7.1, 1.5Hz, 1H), 7.48 (dd, J=8.3, 1.4Hz, 1H), 7.38 (ddd, J=8. 5, 7.1, 1.4Hz, 1H).

Compound PLC-4.2: PLC-4.1 (190 mg, 0.426 mmol), 4-(4-aminophenyl)butanoic acid (180 mg, 0.5 mg) in anhydrous N,N-dimethylformamide (DMF) (4 mL). A mixture of 64 mmol) and 4-(N,N-dimethylamino)-pyridine (4 mg) was heated at 165° C. for 2.5 hours. After cooling to room temperature and standing overnight, the solid was collected by filtration, which was washed with acetone and dried in a vacuum oven at 90 °C for 1 hour to give a yellow solid (220 mg, 84.5% yield). I got it. LCMS ₍ APCI-): Calcd for _C28H17Br2NO5 ( _M- ): 604.95; Found _: 605. ¹ H NMR (400 MHz, DMSO-d ₆ ) δ 9.42 (dd, J = 8.6, 1.5 Hz, 1H), 8.57 (d, J = 4.6 Hz, 2H), 7.83 ~ 7.68 (m, 1H), 7.63 to 7.44 (m, 2H), 7.34 (d, J = 8.3Hz, 2H), 7.31 to 7.16 (m, 2H), 2.67 (dd, J=4.8, 2.8Hz, 2H), 2.28 (t, J=7.4Hz, 2H), 1.95-1.80 (m, 2H).

Compound PLC-4.3: Compound PLC-4.2 (100 mg, 0.165 mmol), (3,5-bis(trifluoromethyl)phenyl)boronic acid (170 mg) in THF/water (5 mL/0.5 mL). , 0.66 mmol), [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride (Pd(dppf)Cl ₂ ) (20 mg, 0.027 mmol), and potassium carbonate (138 mg, 1 mmol). The mixture was degassed and then heated at 80° C. for 2 hours. After cooling to room temperature, the precipitate was collected by filtration, washed with acetone, and then dried in a vacuum oven at 90° C. for 2 hours. A yellow solid (142 mg, 94% yield) was obtained. LCMS ( _APCI- ): Calcd for _C44H23F12NO5 (M-) = _873.14 ; Found: ₈₇₃ . ^1H NMR (400MHz, d2-TCE) δ 8.65 (s, 1H), 8.40 (s, 1H), 8.17 (s, 2H), 7.96 (d, J = 19.3Hz, 4H), 7.38 (d, J=8.4Hz, 1H), 7.33 (d, J=8.0Hz, 2H), 7.18 (d, J=8.0Hz, 3H), 6. 90 (d, J = 6.3 Hz, 2H), 2.72 (t, J = 7.6 Hz, 2H), 2.38 (t, J = 7.4 Hz, 2H), 2.03 to 1.93 (m, 2H).

Compound PLC-4: Compound PLC-1.4 (20 mg, 0.025 mmol), PLC-4.3 (55 mg, 0.0626 mmol), 4-dimethylaminopyridinium/p-toluenesulfonate (DMAP/ A mixture of TsOH salt (30 mg, 0.1 mmol) and N,N'-diisopropylcarbodiimide (DIC) (0.1 mL) was stirred at room temperature for 60 hours. The mixture was loaded onto silica gel and purified by flash chromatography using an eluent of dichloromethane/ethyl acetate (0%→5% ethyl acetate). The desired fractions were collected and concentrated under reduced pressure. The resulting solid was washed with methanol and dried in air to give the desired product as a dark green solid (18 mg, 29% yield). ¹ H NMR (400MHz, d2-TCE) δ 8.64 (s, 2H), 8.40 (s, 2H), 8.16 (s, 4H), 8.05-7.88 (m, 12H) , 7.63 (dd, J=8.6, 2.9Hz, 8H), 7.44-7.32 (m, 6H), 7.27-7.08 (m, 10H), 6.96- 6.83 (m, 6H), 6.79 (t, J=7.6Hz, 4H), 6.70 (d, J=7.4Hz, 4H), 6.47 (s, 2H), 5. 93 (s, 2H), 2.80 (t, J = 7.6Hz, 4H), 2.62 (t, J = 7.2Hz, 4H), 2.17 to 2.03 (m, 4H), 1.92 (s, 6H), 1.78 (s, 3H).

Synthesis of compound: PLC-5:

Compound PLC-5: PLC-2.1 (20 mg, 0.025 mmol), PLC-4.3 (61 mg, 0.07 mmol), 4-dimethylaminopyridinium/p-toluenesulfonate (DMAP/TsOH salt) (20 mg, A mixture of N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (EDC·HCl) (134 mg, 0.7 mmol) was stirred in 5 mL dichloromethane at 40° C. overnight. The resulting mixture was loaded onto silica gel and purified by flash chromatography using an eluent of hexane/ethyl acetate (0%→20% ethyl acetate). The desired fractions were collected and concentrated under reduced pressure. The resulting solid was washed with methanol and dried in air to give the desired product as a dark green solid (20 mg, 32% yield). ^1H NMR (400MHz, d2-TCE) δ 8.64 (s, 2H), 8.39 (s, 2H), 8.16 (d, J = 1.6Hz, 4H), 8.04-7. 87 (m, 12H), 7.64 (d, J=8.3Hz, 4H), 7.49 (s, 2H), 7.45-7.28 (m, 10H), 7.19 (dd, J = 17.8, 8.1Hz, 6H), 7.04 (s, 2H), 6.95 to 6.83 (m, 6H), 6.78 (t, J = 7.4Hz, 4H), 6.69 (d, J=7.3Hz, 4H), 6.47 (s, 2H), 5.94 (s, 2H), 2.80 (t, J=7.8Hz, 4H), 2. 63 (t, J=7.4Hz, 4H), 2.16-2.02 (m, 4H), 1.91 (s, 6H), 1.78 (s, 3H).

Synthesis of compound PLC-6:

Compound PLC-6.1: A mixture of 4-bromo-1,8-naphthalic anhydride (2.77 g, 10 mmol), 4-bromo-2-nitrophenol (3.27 g, 15 mmol) was heated under vacuum for 30 minutes. Degassed and then added anhydrous NMP (50 mL) followed by 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 at 180° C. overnight under an argon atmosphere. After cooling to room temperature, 50 mL of 20% aqueous hydrochloric acid solution was added dropwise to this solution, followed by 50 mL of water. The resulting mixture was left for 3 hours and then filtered to collect the precipitate, which was dried in vacuo to yield 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. Filtered and dried in vacuo to give a tan solid (3.3 g, 80% yield) as the desired product. LCMS ( _APCI +): Calcd for _C18H9BrNO6 (M+H) = _413.95 ; Found: 414. ¹ H NMR (400MHz, TCE-d2) δ 8.70 (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 to 7.79 (m, 2H), 7.20 (d, J = 8.7Hz, 1H), 6.82 (d, J=8.3Hz, 1H).

Compound PLC-6.2: A mixture of compound PLC-6.1 (1.5 g, 3.6 mmol), iron powder (0.60 g, 10.8 mmol) in acetic acid (50 mL) was heated at 125° C. for 30 minutes. did. After cooling to room temperature, 100 mL of water was added to the mixture with stirring. The resulting mixture was filtered, washed with water, and dried in air and vacuum to give a solid (1.35 g, 82% yield). LCMS (APCI-): Calcd for _{C18H10BrNO4 = 382.98} ; Found: 383. ^1H NMR (400MHz, DMSO- _d6 ) δ 9.01-8.26 (m, 3H), 7.96 (s, 1H), 6.93 (dd, J=85.2, 36.5Hz, 4H), 5.54(s, 2H).

Compound PLC-6.3: Compound PLC-6.2 (2.65 g, 6.9 mmol) was dispersed in acetic acid (50 mL)/water (10 mL) and cooled to 0°C. While stirring, pre-chilled hydrochloric acid (2.8 mL, 34.5 mmol) was added, followed by dropwise addition of a solution of sodium nitrite (3.57 g, 52 mmol) in 15 mL of water at 0<0>C. The whole was stirred at 0° C. for 1 hour, then transferred to an additional funnel and added dropwise to a copper sulfate solution (12 g, 47 mmol, 140 mL 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), then stirred in 50 mL of acetone at 40 °C for 30 min, filtered, dried in air and then in vacuo. , a tan solid (1.76 g, 70% yield) was obtained. LCMS ( _APCI +): Calcd for _C18H8BrO4 (M+H) ₌ 366.95; Found: 367. ^1H NMR (400MHz, d2-TCE) δ 8.51 (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).

Compound PLC-6.4: Compound PLC-6.3 (550 mg, 1.5 mmol), 4-(4-aminophenyl)butanoic acid (537 mg, 3 mmol) and DMAP (12.2 mg, 0.5 mmol) in 10 mL of DMF. 1 mmol) of the mixture was heated in a microwave reactor at 165° C. for 2.5 hours. The resulting solution was added dropwise to 50 mL of acetone while stirring. A precipitate formed, filtered, and dried in a vacuum oven at 60° C. overnight to yield the desired product as a tan solid (0.49 g, 62% yield). LCMS (APCI-): Calcd _{for C28H18BrNO5} = _527.04 ; Found: 527. ¹ H NMR (400 MHz, DMSO-d ₆ ) δ 8.54 (d, J = 2.3 Hz, 1H), 8.41 (dd, J = 9.9, 8.0 Hz, 2H), 8.33 ( d, J=7.9Hz, 1H), 7.71 (dd, J=8.8, 2.3Hz, 1H), 7.39 (dd, J=8.6, 4.2Hz, 2H), 7 .25 (d, J=8.0Hz, 2H), 7.17 (d, J=7.9Hz, 2H), 2.63-2.55 (m, 2H), 2.27-2.15 ( m, 2H), 1.87 to 1.73 (m, 2H).

Compound PLC-6.5: Compound PLC-6.4 (385 mg, 0.729 mmol) in cosolvent of THF/DMF/water (20 mL/4 mL/2 mL), 3,5-bis-(trifluoromethyl)phenyl A mixture of boronic acid (374 mg, 1.45 mmol), Pd(dppf) _Cl2 (36 mg, 0.05 mmol), potassium carbonate (276 mg, 2 mmol) was degassed and then heated at 80<0>C overnight. The mixture was worked up with 200 mL of ethyl acetate and 50 mL of 0.6N aqueous hydrochloric acid. The aqueous phase was extracted with ethyl acetate (100 mL x 2). The organic phase was collected, washed with brine (100 mL x 2), dried over sodium sulfate, then dry loaded onto silica gel and eluted with DCM/EA (0% → 40% EA with 0.1% TFA). Purified by flash chromatography using . The main desired fractions were collected and the solvent was removed under reduced pressure to yield a yellow solid (340 mg, 70.5% yield). LCMS (APCI-): Calcd for C ₃₆ H ₂₁ F ₆ NO ₅ = 661.13; Found: 661. ^1H NMR (400MHz, d2-TCE) δ 8.57 (dd, J=19.2, 8.1Hz, 2H), 8.18 (d, J=2.2Hz, 1H), 8.05 (d , J=8.0Hz, 1H), 8.03 to 7.98 (m, 2H), 7.87 (s, 1H), 7.72 (dd, J=8.6, 2.2Hz, 1H) , 7.48 (d, J=8.6Hz, 1H), 7.33 (d, J=8.3Hz, 3H), 7.21-7.12 (m, 2H), 2.72 (t, J=7.6Hz, 2H), 2.39 (t, J=7.3Hz, 2H), 2.04 to 1.97 (m, 2H).

Compound PLC-6: Compound PLC-1.4 (20 mg, 0.025 mmol), Compound PLC-6.5 (52.9 mg, 0.08 mmol), DMAP/TsOH salt (20 mg, 0.068 mmol) in 5 mL of DCM. ), EDC·HCl (110 mg, 0.57 mmol) was stirred at room temperature overnight. The resulting mixture was loaded onto silica gel and purified by flash chromatography using an eluent of DCM/ethyl acetate (0%→10% ethyl acetate). The desired red fraction was collected. After removing the solvent, the solid was washed with methanol and dried in air to give the desired product as a dark solid (34 mg, 65% yield). Confirmed by ¹ H NMR (400 MHz, methylene chloride-d ₂ ) δ 8.64 (d, J = 7.8 Hz, 2H), 8.57 (d, J = 8.3 Hz, 2H), 8.28 ( d, J = 2.2Hz, 2H), 8.17 (s, 4H), 8.11 to 7.96 (m, 8H), 7.83 (dd, J = 8.6, 2.2Hz, 2H ), 7.78-7.70 (m, 8H), 7.55 (d, J=8.6Hz, 2H), 7.52-7.45 (m, 4H), 7.37-7.28 (m, 6H), 7.27-7.20 (m, 4H), 7.05-6.97 (m, 2H), 6.92 (dd, J=8.4, 6.7Hz, 4H) , 6.88-6.81 (m, 4H), 6.58 (s, 2H), 6.08 (s, 2H), 2.92 (t, J=7.7Hz, 4H), 2.75 (t, J=7.4Hz, 4H), 2.23 (p, J=7.6Hz, 4H), 2.06 (s, 6H), 1.91 (s, 3H).

Synthesis of compound PLC-7:

Compound PLC-7.1: PLC-1.7 (1H,3H-isochromeno[6,5,4-mna]xanthene-1,3-dione) (100 mg, 0.347 mmol), 2- A mixture of (4-aminophenyl)acetic acid (135 mg, 0.9 mmol) was heated at 165° C. for 2 hours in a microwave reactor. After cooling to 50 °C, 1.5 mL of acetone was added dropwise to the resulting solution to form a yellow precipitate, which was collected by filtration, then washed with acetone and dried in air to give a yellow solid ( 88 mg, 61% yield) was obtained. Confirmed _by LCMS (APCI): Calcd for _{C26H15NO5 (} M-): 421.1; Found: 421. ¹ H NMR (400 MHz, DMSO-d ₆ ) δ 8.27 (d, J=45.1 Hz, 4H), 7.67-7.00 (m, 8H), 3.58 (s, 2H).

Compound PLC-7: Compound PLC-1.4 (40 mg, 0.05 mmol), Compound PLC-7.1 (67 mg, 0.16 mmol), DMAP/TsOH salt (20 mg, 0.068 mmol) in 10 mL of DCM, A mixture of EDC.HCl (110 mg, 0.57 mmol) was stirred at room temperature overnight and then heated at 40° C. overnight. The resulting mixture was loaded onto silica gel and purified by flash chromatography using an eluent of DCM/ethyl acetate (0%→10% ethyl acetate). The desired red fraction was collected. After removing the solvent, the solid was triturated with methanol and dried in air to give the desired product as a dark solid (38 mg, 47% yield). Confirmed by ^1H NMR (400MHz, d2-TCE) δ 8.46 (dd, J = 19.0, 8.1Hz, 4H), 7.99 (d, J = 8.3Hz, 6H), 7.81 (d, J=8.2Hz, 2H), 7.67-7.60 (m, 8H), 7.56 (d, J=8.2Hz, 4H), 7.51 (t, J=7. 7Hz, 2H), 7.35-7.26 (m, 8H), 7.18 (dd, J = 8.5, 2.0Hz, 6H), 6.87 (d, J = 7.6Hz, 2H ), 6.79 (t, J = 7.5 Hz, 4H), 6.71 (d, J = 7.3 Hz, 4H), 6.48 (s, 2H), 5.93 (s, 2H), 3.95 (s, 4H), 1.92 (s, 6H), 1.78 (s, 3H).

Synthesis of compound PLC-8:

Compound PLC-8.1: Compound PLC-6.4 (649 mg, 1.23 mmol), 4-(trifluoromethyl)phenylboronic acid (467 mg) in cosolvent of THF/DMF/water (30 mL/6 mL/3 mL). , 2.46 mmol), Pd(dppf) _Cl2 (45 mg, 0.06 mmol), potassium carbonate (345 mg, 2.5 mmol) was degassed and then heated at 80<0>C overnight. The mixture was worked up with 300 mL of ethyl acetate and 50 mL of 0.6N aqueous hydrochloric acid. The aqueous phase was extracted with ethyl acetate (150 mL x 3). The organic phase was collected, washed with brine (100 mL x 2), dried over sodium sulfate, then dry loaded onto silica gel and diluted with DCM/EA (0% → 80% EA with 0.1% TFA). ) was purified by flash chromatography using an eluent of The main desired fractions were collected and the solvent removed under reduced pressure to yield a yellow solid (414 mg, 57% yield). ^1H NMR (400MHz, d2-TCE) δ 8.55 (dd, J=18.1, 8.1Hz, 2H), 8.16 (d, J=2.2Hz, 1H), 8.00 (d , J=8.1Hz, 1H), 7.68 (dd, J=8.6, 2.1Hz, 1H), 7.66 to 7.59 (m, 2H), 7.43 (d, J= 8.6Hz, 1H), 7.32 (tt, J = 8.2, 4.2Hz, 5H), 7.20 to 7.13 (m, 2H), 2.72 (t, J = 7.6Hz) , 2H), 2.39 (t, J = 7.3Hz, 2H), 1.99 (q, J = 7.4Hz, 2H).

Compound PLC-8: Compound PLC-1.4 (26 mg, 0.0326 mmol), Compound PLC-8.1 (59 mg, 0.1 mmol), DMAP/TsOH salt (15 mg, 0.051 mmol) in 5 mL of DCM, A mixture of EDC.HCl (60 mg, 0.31 mmol) was stirred at room temperature overnight. The resulting mixture was loaded onto silica gel and purified by flash chromatography using an eluent of DCM/ethyl acetate (0%→10% ethyl acetate). The desired red fraction was collected. After removing the solvent, the solid was washed with methanol and dried in air to give the desired product as a dark solid (46 mg, 72% yield). ^1H NMR (400MHz, d2-TCE) δ 8.51 (dd, J = 18.1, 8.1Hz, 4H), 8.11 (d, J = 2.2Hz, 2H), 7.97 (dd , J = 17.1, 8.2Hz, 6H), 7.71-7.56 (m, 14H), 7.39 (dd, J = 10.8, 8.4Hz, 6H), 7.27 ( dd, J=13.0, 8.3Hz, 6H), 7.23-7.17 (m, 4H), 7.17-7.10 (m, 4H), 6.94-6.84 (m , 2H), 6.79 (t, J = 7.5Hz, 4H), 6.70 (d, J = 7.1Hz, 4H), 6.48 (s, 2H), 5.93 (s, 2H) ), 2.80 (t, J=7.5Hz, 4H), 2.63 (t, J=7.3Hz, 4H), 2.12 (q, J=7.6Hz, 4H), 1.92 (s, 6H), 1.78 (s, 3H).

Synthesis of compound PLC-9:

Compound PLC-9.1: 2-(9-bromo-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)acetic acid. Compound PLC-6.3 (6.3 g, 17.159 mmol, 1 eq.) was suspended in 35 mL of anhydrous DMSO and glycine (2.31 g, 30.77 mmol, 1.8 eq.) was added to the reaction mixture at room temperature. . The resulting mixture was stirred at 130° C. for 1 hour (the mixture did not dissolve), then it was heated to 160° C. for 1 hour, and LMCMS showed the reaction was complete. After cooling to room temperature, the solid product was filtered, washed with water (250 mL), and then dried in a vacuum oven to yield 6.5 g of a greenish yellow solid (90% yield). MS (APCI): Calculated for formula C ₂₀ H ₁₀ BrNO ₅ (M-) = 424; Found: 424. ^1H NMR (400MHz, DMSO-d6) δ 8.65 (s, 1H), 8.50 (s, 1H), 8.46 (d, J=8.2Hz, 2H), 8.09 (d, J = 8.0Hz, 2H), 7.99 (d, J = 8.7Hz, 1H), 7.87 (d, J = 8.0Hz, 2H), 7.58 (d, J = 8.6Hz) , 1H), 7.45 (d, J = 8.4Hz, 1H), 4.71 (s, 2H).

Compound PLC-9.2 2-(9-(4-(tert-butyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)acetic acid (Compound PLC-9.1) (4.24 g, 10.0 mmol, 1 equivalent) was suspended in 2-methyl-THF (150 ml), H ₂ O (5.0 ml), and 4-(tert-butyl)phenyl Boronic acid (3.56 _g , 20 mmol, 2 eq.), _K2CO3 (2.76 g, 20 mmol, 2 eq.), Pd(dppf) _Cl2.DCM (163.3 mg, 0.2 mmol, 0.02 eq.) added. The reaction mixture was degassed three times using a Vac-Fill argon cycle and heated and stirred at 95° C. for 12 hours under an argon atmosphere. After cooling to room temperature, ethyl acetate (150 ml) acidified to pH 4-5 with 1N HCl was added. The organic layer was washed with water, separated and concentrated. The residue was stirred in DMF (15 ml) and filtered to give a solid, which was washed with MeOH (50 mL) and then dried in a vacuum oven to give 4.1 g of a greenish yellow solid product ( A yield of 85% was obtained. MS (APCI): Calculated for formula C ₃₀ H ₂₃ NO ₅ (M-) = 477; Found: 477. ^1H NMR (400MHz, DMSO-d6) δ 8.33 (d, J = 6.1Hz, 3H), 8.24 (d, J = 7.9Hz, 1H), 7.95 (s, 1H), 7.78 (d, J = 8.3Hz, 1H), 7.70 (d, J = 7.9Hz, 2H), 7.50 (d, J = 7.9Hz, 2H), 7.39 (d , J = 8.3Hz, 1H), 7.29 (d, J = 8.2Hz, 1H), 4.52 (s, 2H), 2.89 (s, 3H), 2.73 (s, 3H) ), 2.54-2.47 (m, 21H), 1.34 (s, 10H).

Compound PLC-9: (5,5-difluoro-10-mesityl-1,9-diphenyl-5H-4λ ⁴ ,5λ ⁴ -dipyrrolo[1,2-c:2',1'-f][1,3 ,2]diazaborinine-3,7-diyl)bis([1,1'-biphenyl]-4',4-diyl)bis(2-(9-(4-(tert-butyl)phenyl)-1,3 -dioxo-1H-xanteno[2,1,9-def]isoquinolin-2(3H)-yl)acetate): Compound PLC-9.2 (143.25 mg, 0.30 mmol, 3 eq.) was dissolved in anhydrous DCM (10 .0ml), PLC-1.4 (39.93mg, 0.05mmol, 1eq), DMAP-pTSA (58.8mg, 0.2mmol, 4eq), EDC・HCl (47.92mg, 0 .25 mmol, 5 eq.), stirred at room temperature under argon atmosphere for 5 h, diluted with DCM (150 ml), filtered, washed the solid with 50 ml DCM, collected the filtrate, and transferred to _an 80 g SiO column. and eluted with Hex-DCM (1/1), DCM only, then 0.5% EA in DCM. The good fractions were concentrated and then washed with MeOH to give 79 mg, 91% yield. ¹ H NMR (400 MHz,) δ 8.62 (d, J = 7.9 Hz, 2H), 8.56 (d, J = 8.4 Hz, 2H), 8.19 (d, J = 2.1 Hz, 2H), 8.04-7.97 (m, 3H), 7.95 (s, 4H), 7.71 (dd, J=8.6, 2.1Hz, 2H), 7.61 (dd, J = 8.6, 1.9Hz, 8H), 7.57 to 7.53 (m, 4H), 7.45 (d, J = 8.5Hz, 4H), 7.40 (d, J = 8 .6Hz, 2H), 7.29 (d, J = 8.3Hz, 2H), 7.20 (d, J = 8.6Hz, 5H), 6.86 (d, J = 7.5Hz, 3H) , 6.78 (t, J=7.5Hz, 4H), 6.69 (d, J=7.2Hz, 4H), 6.46 (s, 2H), 5.14 (s, 5H), 1 .91 (s, 7H), 1.77 (s, 4H), 1.31 (s, 18H).

Synthesis of compound PLC-10:

Compound PLC-10.1:2-(1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl) Acetic acid. Compound PLC-9.1 (7.0 g, 16.50 mmol, 1 eq.) was suspended in 2-methyl-THF (150 mL), and 4-(trifluoromethyl)benzeneboronic acid (5.648 g, 29.7 mmol, 1.8 eq.), _K2CO3 (4.65 _g , 33 mmol, 2 eq.), _H2O (15 mL), Pd(dppf) _Cl2.DCM (269.5 mg, 0.33 mmol, 0.02 eq.) added. Three Vac-Fill Argon cycles, the resulting mixture was stirred and heated at 95 °C for 12 h under an argon atmosphere, the mixture was cooled to room temperature and treated with 1N HCl (20 mL). Stir for 15 minutes and then hold at room temperature for 1 hour. The solid was filtered and stirred with DMF for 15 minutes at room temperature, then filtered and the greenish yellow solid was washed with MeOH and then dried in a vacuum oven to yield 6.70 g of a greenish yellow solid, This was used in the next step without further purification (83% yield). MS (APCI): Calculated for formula C ₂₇ H ₁₄ FNO ₅ (M-) = 489; Found: 489. ^1H NMR (400MHz, DMSO-d6) δ 8.52 (s, 1H), 8.37 (q, J = 8.1, 7.7Hz, 3H), 8.04 (d, J = 7.9Hz , 2H), 7.93 (d, J = 8.7Hz, 1H), 7.84 (d, J = 8.0Hz, 2H), 7.49 (d, J = 8.6Hz, 1H), 7 .34 (d, J=8.3Hz, 1H), 4.67 (s, 2H).

Compound PLC-10: (5,5-difluoro-10-mesityl-1,9-diphenyl-5H-4λ ⁴ ,5λ ⁴ -dipyrrolo[1,2-c:2',1'-f][1,3 ,2]diazaborinine-3,7-diyl)bis([1,1'-biphenyl]-4',4-diyl)bis(2-1,3-dioxo-9-(4-(trifluoromethyl)phenyl) )-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)acetate). Compound PLC-10.1 (73.4 mg, 0.15 mmol, 3 eq.) was suspended in anhydrous DCM (10.0 ml), compound PLC-1.4 (39.93 mg, 0.05 mmol, 1 eq.), DMAP - Add pTSA (58.8 mg, 0.2 mmol, 4 eq.), EDC.HCl (47.92 mg, 0.25 mmol, 5 eq.), stir at room temperature under argon atmosphere for 5 hours, and dilute with DCM (150 ml). filtered, washed the solid with 50 ml DCM, collected the filtrate and loaded onto a 80 g _SiO2 column, eluting with Hex-DCM (1/1), DCM only, then 0.5% EA in DCM. and then washed with MeOH to give 82 mg, 94% yield. ^1H NMR (400MHz) δ 8.63 (d, J = 7.9Hz, 1H), 8.58 (d, J = 8.3Hz, 1H), 8.19 (d, J = 2.1Hz, 1H ), 8.01 (d, J = 8.2 Hz, 1H), 7.96 (d, J = 8.3 Hz, 2H), 7.71 (d, J = 2.5 Hz, 4H), 7.61 (d, J=8.1Hz, 3H), 7.45 (d, J=8.6Hz, 1H), 7.32 (d, J=8.4Hz, 1H), 7.20 (d, J= 8.6Hz, 2H), 6.87 (t, J = 7.3Hz, 1H), 6.78 (t, J = 7.6Hz, 2H), 6.69 (d, J = 7.5Hz, 2H) ), 6.45 (s, 2H), 5.24 (s, 1H), 5.14 (s, 2H), 1.96 (s, 1H), 1.91 (s, 3H), 1.77 (s, 2H), 1.18 (d, J=6.5Hz, 6H).

Synthesis of compound PLC-11:

Compound PLC-11.1: (3,7-bis(4-bromophenyl)-10-(2,6-dichlorophenyl)-5,5-difluoro-1,9-diphenyl-5H-4l4,5l4-dipyrrolo[ 1,2-c:2',1'-f][1,3,2]diazaborinine): A 250 mL 2N round bottom flask was placed in an aluminum heat block, and a stir bar was placed in it. The flask was fitted with a finned condenser/gas adapter and a flow control valve. The system was flushed with argon. 2-(4-Bromophenyl)-4-phenyl-1H-pyrrole (3.00 mmol, 895 mg) and 2,6-dichlorobenzaldehyde (1.530 mmol, 268 mg) were added to the flask, followed by anhydrous dichloroethane (40 mL). added. Under an argon atmosphere, the reaction mixture was sparged with nitrogen for 2 minutes, then pTsOH.H ₂ O (0.450 mmol, 86 mg) was added followed by an additional 10 mL of anhydrous dichloroethane. TLC shows spot-to-spot conversion to the desired dipyrrolomethane in 15 minutes at room temperature. The nitrogen sparge was discontinued and the reaction mixture was stirred under argon. The reaction mixture was stirred under argon overnight. The next day, DDQ (1.80 mmol, 409 mg) was added followed by anhydrous dichloroethane and the reaction mixture was stirred at room temperature for 1 hour. Et ₃ N (13.5 mmol, 1.7 mL) and BF ₃ .OEt ₂ (9.00 mmol, 1.3 mL) were added to the reaction mixture, and the reaction mixture was stirred at room temperature for 2 minutes. The addition of Et ₃ N (13.5 mmol, 1.7 mL) and BF ₃ .OEt ₂ (9.00 mmol, 1.3 mL) was repeated and the reaction mixture was then stirred at room temperature for 1 h. The heat block was set at 80° C. and the reaction mixture was stirred at this temperature for 1 hour. The reaction mixture was cooled to room temperature, diluted with 300 mL of ethyl acetate, and quenched by the addition of methanol (25 mL). The reaction mixture was extracted with saturated aqueous NaHCO ( ₃ x 100 mL), brine (50 mL), dried over _MgSO , filtered and evaporated to dryness in vacuo. The crude product was dissolved in DCM and evaporated onto approximately 40 mL of flash silica gel in vacuo. Purified by silica gel flash chromatography (220 g, solids, equilibration 50% toluene/hexane, elution 50% toluene/hexane (2 CV) → 75% toluene/hexane (30 CV)). Fractions containing product were evaporated to dryness in vacuo. Obtained 748 mg of a dark pink solid, 62% yield (based on pyrrole). MS (APCI): Calculated value (M-) for formula C ₃₉ H ₂₃ BBr ₂ Cl ₂ F ₂ N ₂ = 796; found value: 796. ¹ H NMR (400 MHz, tetrachloroethane-d ₂ ) δ 7.87-7.79 (m, 4H), 7.66-7.59 (m, 4H), 7.03-6.90 (m, 10H) ), 6.57-6.44 (m, 5H).

Compound PLC-11.2: (4',4'''-(10-(2,6-dichlorophenyl)-5,5-difluoro-1,9-diphenyl-5H-4l4,5l4-dipyrrolo[1,2 -c:2',1'-f][1,3,2]diazaborinine-3,7-diyl)bis([1,1'-biphenyl]-4-ol)):PLC-11.2, Similar to the procedure above, PLC-11.1 (0.650 mmol, 519 mg), (4-hydroxyphenyl)boronic acid (3.90 mmol, 538 mg), _K2 in anhydrous THF (100 mL) and water (10 mL) It was synthesized from CO ₃ (15.02 mmol, 2.075 g) and Pd(dppf)Cl ₂ (0.065 mmol, 48 mg). The crude reaction mixture was quenched with acetic acid (10 mL) and flash silica gel (approximately 40 mL) was added. The crude reaction mixture was evaporated to dryness in vacuo. Purified by silica gel flash chromatography (120 g, equilibration 100% hexane, elution 100% hexane (2 CV) → 100% EtOAc (30 CV)). Fractions containing product were evaporated to dryness in vacuo. 501 mg (93% yield) of a dark solid was obtained. MS (APCI): Calculated value (M-) for formula C ₅₁ H ₃₃ BCl ₂ F ₂ N ₂ O ₂ = 824; found value: 824. ¹ H NMR (400 MHz, tetrachloroethane-d ₂ ) δ 8.10-8.01 (m, 4H), 7.73-7.64 (m, 4H), 7.63-7.54 (m, 4H) ), 7.08-6.89 (m, 14H), 6.62-6.45 (m, 5H).

Compound PLC-11: ((10-(2,6-dichlorophenyl)-5,5-difluoro-1,9-diphenyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f ][1,3,2]diazaborinine-3,7-diyl)bis([1,1'-biphenyl]-4',4-diyl)bis(4-(4-(1,3-dioxo-1H- xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)butanoate): PLC-11 was prepared as PLC-11.2 (0.100 mmol, 83 mg) in anhydrous EtOAc (5 mL), It was synthesized from PLC-1.8 (0.300 mmol, 135 mg), DMAP・pTsOH salt (0.400 mmol, 118 mg), and EDC・HCl (0.250 mmol, 48 mg). The addition of EDC.HCl (0.250 mmol, 48 mg) was repeated to obtain a complete reaction. The reaction mixture was evaporated to dryness in vacuo, dissolved in DCM, loaded onto flash silica gel (approximately 40 mL in a solids loader) and subjected to silica gel flash chromatography (120 g, equilibration 100% DCM, elution 100% DCM (2 CV) → 10 % EtOAc/DCM (30 CV)). Fractions containing product were evaporated to dryness in vacuo. 116 mg (69% yield) was obtained. MS (APCI): Calculated value (M-) for formula C ₁₀₇ H ₆₇ BCl ₂ F ₂ N ₄ O ₁₀ = 1686; found value: 1686. ¹ H NMR (400 MHz, methylene chloride-d ₂ ) δ 8.65 (d, J = 7.9 Hz, 2H), 8.60 (d, J = 8.3 Hz, 2H), 8.22 (s, 4H ), 8.14 (dd, J = 8.0, 1.6 Hz, 2H), 8.02 (d, J = 8.0 Hz, 2H), 7.74 to 7.67 (m, 4H), 7 .63-7.54 (m, 6H), 7.50 (s, 4H), 7.46-7.30 (m, 18H), 7.29-7.24 (m, 4H), 7.20 ~7.13 (m, 4H), 7.06 ~ 7.00 (m, 8H), 4.04 (s, 4H), 2.76 (hept, J=7.0Hz, 4H), 1.16 (d, J=6.8Hz, 24H).

Synthesis of compound PLC-12:

Compound PLC-12.1: 1H,3H-isochromeno[6,5,4-mna]xanthene-1,3-dione (compound PLC-1.7) (100 mg, 0.347 mmol) in 5 mL DMF, 2 A mixture of -(4-aminophenyl)acetic acid (135 mg, 0.9 mmol) was heated at 165° C. for 2 hours in a microwave reactor. After cooling to 50 °C, 1.5 mL of acetone was added dropwise to the resulting solution to form a yellow precipitate, which was collected by filtration, then washed with acetone and dried in air to give a yellow solid ( 88 mg, 61% yield) was obtained. Confirmed _by LCMS (APCI): Calcd for _{C26H15NO5 (} M-): 421.1; Found: 421. ¹ H NMR (400 MHz, DMSO-d ₆ ) δ 8.27 (d, J=45.1 Hz, 4H), 7.67-7.00 (m, 8H), 3.58 (s, 2H).

Compound PLC-12 ((10-(2,6-dichlorophenyl)-5,5-difluoro-1,9-diphenyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f] [1,3,2]diazaborinine-3,7-diyl)bis([1,1'-biphenyl]-4',4-diyl)bis(2-(4-(1,3-dioxo-1H-xantheno) [2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate)): PLC-12 was converted into PLC-12.1 (0.020 mmol, 16.5 mg), 2-(4-( 1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid (0.060 mmol, 25.3 mg), DMAP pTsOH salt (0.080 mmol, 23 .6mg) and EDC·HCl (0.060mmol, 11.5mg). The crude reaction mixture was evaporated to dryness, dissolved in DCM and loaded onto flash silica gel (approximately 5 g) in a solid loader. Purified by silica gel flash chromatography (80 g, equilibrated in 100% DCM, elution 100% DCM (2 CV) → 10% EtOAc/DCM (30 CV)). Fractions containing product were evaporated to dryness and then triturated with hot methanol. The solids were filtered off and dried in a vacuum oven at about 110°C. 19.8 mg (61% yield) of a blueish solid was obtained. MS (APCI): Calculated value (M-) for formula C ₁₀₃ H ₅₉ BCl ₂ F ₂ N ₄ O ₁₀ = 1630; found value: 1630. ^1H NMR (400MHz, methylene chloride-d ₂ ) δ 8.45-8.34 (m, 4H), 8.04 (d, J = 8.1Hz, 4H), 7.93-7.84 (m , 2H), 7.78-7.65 (m, 10H), 7.61 (d, J=8.0Hz, 4H), 7.56-7.46 (m, 2H), 7.40-7 .21 (m, 12H), 7.12-7.01 (m, 6H), 7.01-6.92 (m, 6H), 6.64-6.46 (m, 5H), 4.03 (s, 4H).

Synthesis of compound PLC-13:

Compound PLC-13.1 (6-(4-(tert-butyl)-2-nitrophenoxy)-1H,3H-benzo[de]isochromene-1,3-dione): A 1 L 2N round bottom flask made of aluminum was placed in a heat block, and a stirrer was added. The flask was equipped with a finned condenser/gas adapter, a stopper, and a flow control valve. The system was flushed with argon. 6-bromo-1H,3H-benzo[de]isochromene-1,3-dione (40.0 mmol, 11.084 g) and 4-(tert-butyl)-2-nitrophenol (60.0 mmol, 11.0 mmol) were placed in a flask. 712 g) was added followed by anhydrous NMP (150 mL). NaOH (20.0 mmol, 800 mg) and copper (powder) (20.0 mmol, 1271 mg) were added to the flask, followed by anhydrous NMP (25 mL). The flask was stirred under an argon atmosphere with the heat block set at 170°C. The reaction was stirred at this temperature overnight. The reaction mixture was cooled to room temperature and treated with water (175 mL) and 1N HCl (44 mL). The reaction mixture was stirred for 30 minutes, then filtered off and washed with water. The precipitate was transferred to a flask with acetone/DCM, evaporated to dryness, and then azeotropically mixed with toluene. The crude product was dissolved in a small amount of DCM and treated with methanol (300 mL). DCM and some of the methanol were removed by rotary evaporation using a hot water bath (80° C.). Once all DCM was removed, the mixture was cooled to room temperature and the solids were filtered off. 8.180 g of an amber powder (52% yield) was obtained. MS (APCI): Calculated for formula _C22H17NO6 ( _M +H) = ₃₉₂ ; Found: 392. ^1H NMR (400MHz, tetrachloroethane- _d2 ) δ 8.82 (dd, J=8.4, 1.2Hz, 1H), 8.71 (dd, J=7.3, 1.2Hz, 1H) , 8.49 (d, J = 8.3 Hz, 1H), 8.16 (d, J = 2.4 Hz, 1H), 7.91 (dd, J = 8.4, 7.3 Hz, 1H), 7.80 (dd, J=8.6, 2.4Hz, 1H), 7.34 (d, J=8.6Hz, 1H), 6.91 (d, J=8.3Hz, 1H), 1 .43 (s, 9H).

Compound PLC-13.2 (6-(2-amino-4-(tert-butyl)phenoxy)-1H,3H-benzo[de]isochromene-1,3-dione): A 250 mL 2N round bottom flask made of aluminum. was placed in a heat block, and a stirrer was added. The flask was equipped with a finned condenser/gas adapter, a stopper, and a flow control valve. The system was flushed with argon. Compound 13.1 (10.0 mmol, 3.914 g) and 2-MeTHF (70 mL) were added to the flask. HCl (100 mmol, 4.0 N, 25 mL) and _SnCl2.2H2O ( _40.0 mmol, 9.024 g) in water were added with stirring at room temperature. The reaction mixture was stirred for 30 minutes under an argon atmosphere with the heat block set at 90°C. The reaction mixture was cooled to 0° C. and made basic to pH ˜8 (pH paper) using 2N aqueous NaOH. The solid was filtered off (slow filtration) and the resulting solid was then washed with 2-MeTHF (8 x 100 mL). The filtrate was transferred to a separatory funnel and the layers were separated. The organic layer was dried with _MgSO4 , filtered and evaporated to dryness in vacuo. 3.743 g (quantitative yield) was obtained. Used in next step without further purification. MS (APCI): Calculated for formula _C22H19NO4 ( _M +H) = ₃₆₂ ; Found: 362. ^1H NMR (400MHz, tetrachloroethane- _d2 ) δ 8.88 (dd, J=8.4, 1.2Hz, 1H), 8.69 (dd, J=7.3, 1.2Hz, 1H) , 8.48 (d, J=8.4Hz, 1H), 7.89 (dd, J=8.4, 7.3Hz, 1H), 7.03 to 6.93 (m, 3H), 6. 88 (dd, J=8.4, 2.3Hz, 1H), 1.35 (s, 9H).

Compound PLC-13.3 (9-(tert-butyl)-1H,3H-isochromeno[6,5,4-mna]xanthene-1,3-dione): A 40 mL vial with a stir bar, NaNO ₂ (30. 0 mmol, 2.070 g) and water (10 mL) were added. The vial was stirred in an ice water bath at 0°C. A stir bar and compound 13.2 (4.00 mmol, 1.446 g) were placed in a 100 mL round bottom flask. Ice AcOH (30 mL) and concentrated HCl (20.0 mmol, 12.1 N, 1.65 mL) were added to the flask. The mixture was stirred at room temperature for several minutes, then placed in an ice water bath and stirred for about 1 minute. The solution of _NaNO2 was started to be added before the acetic acid started to freeze. _NaNO2 was added over approximately 10 minutes. The diazo solution was stirred at 0°C for 1 hour. A 250 mL 2N round bottom flask containing a large stir bar was prepared while stirring the diazo solution. The flask was fitted with a finned condenser and addition funnel. The flask was clamped with an off-center neck and the addition funnel was placed on the off-center neck so that the solution hits the top of the vortex when stirred. CuSO ₄ .5H ₂ O (27.4 mmol, 6.842 g) and water (80 mL) were added to the flask. Approximately 15 minutes before the diazo solution was obtained, heating the copper solution to 130°C was started. When the solution reached 130° C., the diazo solution was transferred to an addition funnel and the diazo solution was added dropwise with rapid stirring over a period of approximately 30 minutes. Once the addition was complete, the solution was heated for an additional 1-2 minutes and then cooled in a room temperature water bath. The precipitate was filtered off and washed with water. The precipitate was dried by suction, then the crude precipitate was dissolved/suspended in DCM and evaporated to dryness onto about 10 g of flash silica gel. Silica gel flash chromatography (220 g, solids, equilibration 50% DCM/Hexane, elution 50% DCM/Hexane (2 CV) → 100% DCM (20 CV) → Isocratic DCM (15 CV) → 0% EtOAc/DCM (0 CV) )→1% EtOAc/DCM (10 CV)). product tail. Fractions containing product were evaporated to dryness in vacuo. Obtained 528 mg (38% yield). MS (APCI): Calculated for formula _C22H16O4 ( _M +H) = ₃₄₅ ; Found: 345. ¹ H NMR (400 MHz, tetrachloroethane-d ₂ ) δ 8.61 (d, J = 7.9 Hz, 1H), 8.56 (d, J = 8.4 Hz, 1H), 8.05 (d, J = 2.2Hz, 1H), 8.01 (d, J = 8.0Hz, 1H), 7.66 (dd, J = 8.8, 2.2Hz, 1H), 7.38 (d, J = 8.7Hz, 1H), 7.34 (d, J=8.4Hz, 1H), 1.44 (s, 9H).

Compound PLC-13.4: (4-(4-(9-(tert-butyl)-1,3-dioxo-1H-xanteno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl ) Butanoic acid): Compound 13.4 was prepared in a similar manner to the above procedure as Compound 13.3 (1.525 mmol, 525 mg), 4-(4-aminophenyl)butanoic acid (3.05 mmol, 546 mg), and DMAP. (0.111 mmol, 14 mg). The crude reaction mixture was diluted with acetone (25 mL) and water (50 mL). The resulting precipitate was filtered off and washed with 1:1 acetone:water. The resulting solid was dried in a vacuum oven at about 110°C. 738 mg (96% yield) of a yellow solid was obtained. MS (APCI): Calculated for formula C ₃₂ H ₂₇ NO ₅ (M+H) = 506; Found: 506. ^1H NMR (400MHz, DMSO- _d6 ) δ 12.12 (s, 1H), 8.48-8.29 (m, 3H), 8.23 (d, J=2.3Hz, 1H), 7 .68 (dd, J=8.8, 2.3Hz, 1H), 7.43-7.30 (m, 4H), 7.25 (d, J=7.9Hz, 2H), 2.75- 2.64 (m, 2H), 2.30 (t, J=7.4Hz, 2H), 1.88 (p, J=7.5Hz, 2H), 1.41 (s, 9H).

Compound PLC-13 ((5,5-difluoro-10-mesityl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-3,7 -diyl)bis([1,1'-biphenyl]-4',4-diyl)bis(4-(4-(9-(tert-butyl)-1,3-dioxo-1H-xanteno[2,1 ,9-def]isoquinolin-2(3H)-yl)phenyl)butanoate) 5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-3,7-diyl)bis([1,1'-biphenyl]-4- (compound PLC-1.4) (0.050 mmol, 39.9 mg), PLC-13.4 (0.150 mmol, 75.8 mg), DMAP pTsOH salt (0.200 mmol, 58.9 mg), and Synthesized from EDC·HCl (0.150 mmol, 28.8 mg). The crude reaction mixture was diluted 2:1 with hexane and loaded onto approximately 15 g of flash silica gel in a solids loader. Purified by silica gel flash chromatography (120 g, solids, equilibrated 40% DCM/hexanes, elution 40% DCM/hexanes (2 CV) → 100% DCM (10 CV) → isocratic DCM + 1% EtOAc modifier). Fractions containing product were evaporated to dryness in vacuo. The product was triturated with hot MeOH and the resulting solid was dried in a vacuum oven at about 110°C. Obtained 78.8 mg of a dark red solid (89% yield). MS (APCI): Calculated value (M-) for formula C ₁₀₆ H ₈₃ BF ₂ N ₄ O ₁₀ = 1773; Found value: 1773. ¹ H NMR (400 MHz, tetrachloroethane-d ₂ ) δ 8.61 (d, J = 7.9 Hz, 2H), 8.56 (d, J = 8.3 Hz, 2H), 8.08 (d, J = 8.3Hz, 4H), 8.06 (d, J = 2.3Hz, 2H), 7.99 (d, J = 8.1Hz, 2H), 7.76 to 7.68 (m, 8H) , 7.63 (dd, J = 8.7, 2.2 Hz, 2H), 7.47 (d, J = 8.3 Hz, 4H), 7.36 (d, J = 8.7 Hz, 2H), 7.30 (dd, J=8.3, 1.7Hz, 6H), 7.26-7.20 (m, 4H), 7.01-6.94 (m, 2H), 6.88 (t , J=7.5Hz, 4H), 6.80 (d, J=7.0Hz, 4H), 6.57 (s, 2H), 6.02 (s, 2H), 2.89 (t, J =7.6Hz, 4H), 2.72 (t, J = 7.4Hz, 4H), 2.20 (p, J = 7.5Hz, 4H), 2.01 (s, 6H), 1.87 (s, 3H), 1.45 (s, 18H).

Synthesis of compound PLC-14:

Compound PLC-14.1: (2-(4-(9-(tert-butyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl ) acetic acid): Compound PLC-14.1 was mixed with compound PLC-13.3 (1.191 mmol, 410 mg) and 2-(4-aminophenyl) acetic acid in anhydrous DMF (10 mL) in the same manner as compound 1. (2.98 mmol, 450 mg). After work-up and precipitation, 579 mg of product (quantitative yield) was obtained. MS (APCI): Calculated for formula _C30H23NO5 ( _M +H) = ₄₇₈ ; Found: 478. ¹ H NMR (400 MHz, DMSO-d ₆ ) δ 8.48 (d, J=7.9 Hz, 1H), 8.44 (d, J=8.3 Hz, 1H), 8.38 (d, J= 8.1Hz, 1H), 8.27 (d, J = 2.4Hz, 1H), 7.69 (dd, J = 8.8, 2.3Hz, 1H), 7.45 to 7.38 (m , 4H), 7.31-7.27 (m, 2H), 3.68 (s, 2H), 1.41 (s, 9H).

Compound PLC-14 ((5,5-difluoro-10-mesityl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-3,7 -diyl)bis([1,1'-biphenyl]-4',4-diyl)bis(2-(4-(9-(tert-butyl)-1,3-dioxo-1H-xanteno[2,1 ,9-def]isoquinolin-2(3H)-yl)phenyl)acetate)): Compound PLC-14 was converted to 4',4'''-(5,5-difluoro-10 -Mesityl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-3,7-diyl)bis([1,1'-biphenyl] -4-ol) (PLC-1.4) (0.050 mmol, 39.9 mg), compound PLC-14.1 (0.150 mmol, 71.6 mg), DMAP pTsOH salt (0.200 mmol, 58.9 mg) ), and EDC·HCl (0.150 mmol, 28.8 mg). After purification by conventional methods, the product was triturated with hot MeOH. The product was dried in a vacuum oven at about 110°C. 57.3 mg (67% yield) of a dark red solid was obtained. MS (APCI): Calculated (M-) for formula C ₁₀₂ H ₇₅ BF ₂ N ₄ O ₁₀ = 1716; Found: 1716. ¹ H NMR (400 MHz, tetrachloroethane-d ₂ ) δ 8.53 (d, J = 7.9 Hz, 2H), 8.48 (d, J = 8.3 Hz, 2H), 8.05 (d, J = 2.3Hz, 2H), 8.03 to 7.98 (m, 4H), 7.91 (d, J = 8.0Hz, 2H), 7.75 to 7.69 (m, 8H), 7 .65-7.58 (m, 6H), 7.37-7.33 (m, 4H), 7.32 (d, J=8.7Hz, 2H), 7.28-7.23 (m, 4H), 7.18 (d, J=8.3Hz, 2H), 7.00-6.93 (m, 2H), 6.91-6.84 (m, 4H), 6.84-6. 78 (m, 4H), 6.55 (s, 2H), 6.04 (s, 2H), 4.03 (s, 4H), 2.03 (s, 6H), 1.87 (s, 3H) ), 1.45 (s, 18H).

Synthesis of compound PLC-15:

Compound PLC-15.1 ((E)-1-(4-bromophenyl)-3-(4-(tert-butyl)phenyl)prop-2-en-1-one): In a 500 mL round bottom flask, Stir bar, 1-(4-bromophenyl)ethane-1-one (40.0 mmol, 7.960 g), 4-(tert-butyl)benzaldehyde (40.0 mmol, 6.489 g, 6.69 mL), and ethanol (200 proof, 80 mL). KOH (78.4 mmol, 4.399 g) was added with stirring at room temperature. The reaction mixture was stirred vigorously at room temperature. A precipitate formed within 2-3 minutes, so the stirring speed was increased to maintain a stirred slurry. After 30 minutes, TLC shows complete consumption of starting material. The reaction mixture was poured into stirred water (500 mL). The mixture was stirred at room temperature for 5 minutes, then the solids were filtered off and washed with water. The precipitate was dried in a vacuum oven at 110°C overnight. NMR showed the presence of impurities, so the solid was triturated with methanol. As this did not improve the purity, the material was subjected to silica gel column chromatography (330 g, evaporate the mixture onto silica gel, equilibrate 100% hexane, elute 100% hexane (2 CV) → 10% EtOAc/hexane (20 CV) ). Fractions containing the product were evaporated to dryness in vacuo to give an off-white solid. 8.983 g (65% yield) was obtained. MS (APCI): Calculated for formula C ₁₉ H ₁₉ BrO (M+H) = 343; Found: 343. ^1H NMR (400MHz, tetrachloroethane-d ₂ ) δ 7.92-7.85 (m, 2H), 7.79 (d, J = 15.6Hz, 1H), 7.70-7.65 (m , 2H), 7.64-7.59 (m, 2H), 7.47 (d, J = 8.4Hz, 2H), 7.44 (d, J = 15.6Hz, 1H), 1.35 (s, 9H).

Compound PLC-15.2 (1-(4-bromophenyl)-3-(4-(tert-butyl)phenyl)-4-nitrobutan-1-one): Place a stir bar in a 250 mL 2N round bottom flask, A finned condenser, gas adapter, and flow control valve were installed. After flushing the system with argon, PLC-15.1 (8.898 g, 25.92 mmol), ethanol (200 proof, 27 mL), nitromethane (28 mL), and KOH (5.184 mmol, 291 mg) were charged. The reaction mixture was stirred under argon and heated to 95° C. in an aluminum heat block. After 30 minutes, TLC shows complete consumption of starting material. The flask was removed from the heat block and placed in an ice water bath to cool to approximately room temperature. The reaction mixture was partitioned between ethyl acetate (100 mL) and water (100 mL) and a small amount of solid NaCl was added to break the emulsion. The layers were separated and the organic layer was dried over _MgSO4 , filtered and concentrated to dryness in vacuo. The resulting yellow oil was triturated with hexane while warming to yield a solid. The solid was stirred at room temperature overnight, then filtered off and washed with hexane. The resulting off-white solid was dried in a vacuum oven at 80°C. Obtained 9.10 g (87% yield). MS (APCI): Calculated for formula _C20H22BrNO3 ( _M +H) ₌ 404; Found: 404. ¹ H NMR (400 MHz, tetrachloroethane-d ₂ ) δ 7.82-7.75 (m, 2H), 7.66-7.59 (m, 2H), 7.37-7.32 (m, 2H) ), 7.22 to 7.15 (m, 2H), 4.81 (dd, J = 12.5, 6.7Hz, 1H), 4.68 (dd, J = 12.5, 8.0Hz, 1H), 4.16 (p, J = 7.1Hz, 1H), 3.44 (dd, J = 17.9, 6.1Hz, 1H), 3.36 (dd, J = 17.9, 7 .5Hz, 1H), 1.29(s, 9H).

Compound PLC-15.3 (1-(4-bromophenyl)-3-(4-(tert-butyl)phenyl)-4,4-dimethoxybutan-1-one): In a 500 mL round bottom flask, stir bar I put it in. PLC-15.2 (22.51 mmol, 9.10 g) was added to the flask, followed by anhydrous THF (235 mL) and methanol (120 mL). The reaction mixture was stirred vigorously at room temperature and then KOH (58.35 mmol) was added to the flask. The reaction mixture was stirred at room temperature. In a separate 2N 1L round bottom flask, carefully prepare a mixture of H ₂ SO ₄ (25 mL) and methanol (120 mL). Clamp the flask with the off-center neck and carefully stopper. After 90 minutes, the reaction mixture was added to an off-center neck addition funnel. The 1 L flask was cooled in an ice water bath at 0°C. The H ₂ SO ₄ /MeOH mixture was stirred vigorously and the solution was added dropwise. It appears to be outgassing, and the atmosphere above the liquid turns a brownish-orange color. The addition took place over 2.5 hours. The reaction mixture was stirred for an additional hour, then the mixture was transferred to a 2L Erlenmeyer flask. Water (300 mL) was added to the stirred mixture followed by 2N NaOH (approximately 250 mL) to bring the pH to approximately 10. The solution was partitioned with DCM (2 x 300 mL). The combined organic layers were dried with _MgSO4 , filtered and concentrated to dryness in vacuo. The resulting brown oil solidifies overnight. ¹ H NMR shows a mixture of about 75% dimethyl acetal and 25% aldehyde. This mixture was used in the next step without further purification.

Compound PLC-15.4 (2-(4-bromophenyl)-4-(4-(tert-butyl)phenyl)-1H-pyrrole): Place a stirring bar in a 100 mL 2N round-bottomed flask and place in a finned condenser. , gas adapter, and flow control were installed. The system was flushed with argon. To the flask was added crude PLC-15.3 (assuming 100% yield) and NH ₄ OAc (109.4 mmol, 8.432 g) followed by glacial acetic acid (35 mL). The reaction mixture was stirred under argon and heated in an aluminum heat block at 100°C. TLC at 5 hours shows complete consumption of aldehydes and acetals. The reaction mixture was quenched by pouring into stirred water (300 mL). The resulting precipitate was collected by vacuum filtration and washed with water. It was dried in a vacuum oven at about 80°C. 7.56 g of a dark gray solid (95% yield based on compound 1.2) was obtained. MS (APCI): Calculated for formula _C20H20BrN (M+H) ₌ 354; found: 354. ^1H NMR (400MHz, DMSO-d ₆ ) δ 8.49 (s, 1H), 7.56-7.51 (m, 2H), 7.51-7.47 (m, 2H), 7.43 ~7.37 (m, 4H), 7.16 (dd, J=2.7, 1.7Hz, 1H), 6.81 (dd, J=2.8, 1.7Hz, 1H), 1. 35 (s, 9H).

Compound PLC-15.5 (3,7-bis(4-bromophenyl)-1,9-bis(4-(tert-butyl)phenyl)-5,5-difluoro-10-mesityl-5H-4l4,5l4 -dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine): 250 mL 2N round-bottomed flask with stir bar, finned condenser, gas adapter, and flow rate control. was installed. The system was flushed with argon. To the flask were added PLC-15.4 (2.0 mmol, 709 mg), mesitaldehyde (2.50 mmol, 0.369 mL), and anhydrous dichloroethane (50 mL). The reaction mixture was sparged with nitrogen gas for 10 minutes while stirring at room temperature under an argon atmosphere. pTsOH.H ₂ O (0.300 mmol, 57 mg) was added to the flask and stirring and nitrogen gas sparging continued for an additional 10 minutes. The flask was stirred under static argon and heated at 80° C. using an aluminum heat block overnight. The reaction mixture was cooled to room temperature, DDQ (1.70 mmol, 386 mg) was added and stirring was continued at room temperature for 1 hour under argon. Et ₃ N (8.00 mmol, 1.11 mL) and BF ₃ .OEt ₂ (12.0 mmol, 1.48 mL) were added to the reaction mixture. The reaction mixture was stirred at room temperature for 2 minutes, then the addition of Et ₃ N (8.00 mmol, 1.11 mL) and BF ₃ .OEt ₂ (12.0 mmol, 1.48 mL) was repeated. The flask was returned to the heat block and the heat block was set to 80°C. The reaction mixture was stirred at 80°C for 90 minutes. The reaction mixture was cooled to room temperature, then doubled in volume by addition of hexane and continued stirring at room temperature overnight. The reaction mixture was loaded onto 65 g of flash silica gel in a solids loader. Purified by silica gel flash chromatography (330 g, equilibration 100% hexane, elution 100% hexane (2 CV) → 40% toluene/hexane (30 CV)). Fractions containing product were evaporated to dryness in vacuo. 236 mg (27% yield) of a pink-red solid was obtained. MS (APCI): Calculated value (M-) for formula C ₅₀ H ₄₇ BBr ₂ F ₂ N ₂ = 882; Found value: 882. ¹ H NMR (400 MHz, tetrachloroethane-d ₂ ) δ 7.84-7.78 (m, 4H), 7.64-7.59 (m, 4H), 6.89-6.84 (m, 4H) ), 6.69 to 6.63 (m, 4H), 6.45 (s, 2H), 6.02 (s, 2H), 1.97 (s, 6H), 1.88 (s, 3H) , 1.19 (s, 18H).

Compound PLC-15.6(4',4'''-(1,9-bis(4-(tert-butyl)phenyl)-5,5-difluoro-10-mesityl-5H-4l4,5l4-dipyrrolo[ 1,2-c:2',1'-f][1,3,2]diazaborinine-3,7-diyl)bis(([1,1'-biphenyl]-4-ol))): Compound PLC PLC-15.5 (0.205 mmol, 181 mg), (4-hydroxyphenyl)boronic acid in THF (8 mL) and water (0.8 mL) was prepared in a similar manner as compound 10.1. (1.228 mmol, 169 mg), K ₂ CO ₃ (1.228 mmol, 170 mg), and Pd(dppf)Cl ₂ (0.0512 mmol, 37.4 mg) in a microwave synthesizer at 110°C. The crude reaction mixture was loaded onto approximately 65 g of silica gel in a loader. Purified by silica gel flash chromatography (220 g, equilibration 100% toluene, elution 100% toluene (2 CV) → 10% EtOAc/toluene (20 CV)). Fractions containing product were evaporated to dryness in vacuo. 115 mg (62% yield) of a dark purple-red solid was obtained. MS (APCI): Calculated value (M-) for formula C ₆₂ H ₅₇ BF ₂ N ₂ O ₂ = 910; found value: 910. ¹ H NMR (400 MHz, tetrachloroethane-d ₂ ) δ 7.99-7.90 (m, 4H), 7.62-7.54 (m, 4H), 7.54-7.47 (m, 4H) ), 6.89 to 6.82 (m, 4H), 6.81 to 6.75 (m, 4H), 6.65 to 6.56 (m, 4H), 6.45 (s, 2H), 5.94 (s, 2H), 4.94 (s, 2H), 1.91 (s, 6H), 1.80 (s, 3H), 1.11 (s, 18H).

Compound PLC-15 ((1,9-bis(4-(tert-butyl)phenyl)-5,5-difluoro-10-mesityl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1 '-f][1,3,2]diazaborinine-3,7-diyl)bis([1,1'-biphenyl]-4',4-diyl)bis(4-(4-(9-(3, 5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)butanoate)): compound PLC-15, PLC-15.6 (0.0201 mmol, 18.3 mg), 4-(4-(9-(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1 ,9-def]isoquinolin-2(3H)-yl)phenyl)butanoic acid (PLC-6.5) (0.0603 mmol, 38.2 mg), DMAP pTsOH salt (0.0804 mmol, 23.7 mg), and Synthesized from EDC·HCl (0.0804 mmol, 15.4 mg). The crude reaction mixture was loaded onto approximately 25 g of flash silica gel in a loader. Silica gel flash chromatography (120 g, solids, equilibration 100% hexane, elution 100% hexane (3 CV) → 100% DCM/1% EtOAc modifier (0 CV) → 100% DCM/1% EtOAc modifier (15 CV) ) → 100% DCM/2% EtOAc modifier → 100% DCM/3% EtOAc modifier → 100% DCM/4% EtOAc modifier (follow the separation of the yellow impurity from the product and make sure that they are separate Purified by elution with increasing EtOAc). Fractions containing product were evaporated to dryness in vacuo. 38.6 mg (90% yield) of a dark red solid was obtained. ¹ H NMR (400 MHz, tetrachloroethane-d ₂ ) δ 8.65 (d, J = 7.9 Hz, 2H), 8.59 (d, J = 8.3 Hz, 2H), 8.24 (d, J =2.2Hz, 2H), 8.13 to 8.04 (m, 10H), 7.95 (s, 2H), 7.80 (dd, J = 8.7, 2.1Hz, 2H), 7 .75-7.69 (m, 8H), 7.67-7.62 (m, 4H), 7.56 (d, J=8.6Hz, 2H), 7.41-7.34 (m, 6H), 7.30-7.23 (m, 4H), 6.88 (d, J = 8.4Hz, 4H), 6.70 (d, J = 8.2Hz, 4H), 6.56 ( s, 2H), 6.03 (s, 2H), 4.04 (s, 4H), 2.01 (s, 6H), 1.89 (s, 3H), 1.21 (s, 18H).

Synthesis of compound PLC-16:

Compound PLC-16.1 (3,7-bis(4-bromophenyl)-1,9-bis(4-(tert-butyl)phenyl)-10-(2,6-dichlorophenyl)-5,5-difluoro -5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine): PLC-16.1 was treated with anhydrous DCE ( PLC-15.4 (2.0 mmol, 709 mg), 2,6-dichlorobenzaldehyde (1.0 mmol, 175 mg), pTsOH.H ₂ O (0.300 mmol, 57 mg), DDQ (1.30 mmol, 295 mg), Et ₃ N (8.00 mmol, 1.12 mL), and BF ₃ .OEt ₂ (12.0 mmol, 1.48 mL). The dipyrromethane step was performed at room temperature rather than 80°C. The crude reaction mixture was diluted to 2 volumes with hexane and loaded onto approximately 60 g of flash silica gel in a loader. Purified by silica gel flash chromatography (330 g, solids, no equilibration, elution 100% hexane (2 CV) → 50% toluene/hexane (20 CV)). Fractions containing product were evaporated to dryness in vacuo. 483 mg (53% yield) of a dark red-pink solid was obtained. MS (APCI): Calculated value (M-) for formula C ₄₇ H ₃₉ BBr ₂ Cl ₂ F ₂ N ₂ = 908; found value: 908. ¹ H NMR (400 MHz, tetrachloroethane-d ₂ ) δ 7.87-7.78 (m, 4H), 7.66-7.59 (m, 4H), 6.97-6.87 (m, 8H) ), 6.53-6.37 (m, 5H), 1.18 (s, 18H).

Compound PLC-16.2(4',4'''-(1,9-bis(4-(tert-butyl)phenyl)-10-(2,6-dichlorophenyl)-5,5-difluoro-5H- 4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-3,7-diyl)bis(([1,1'-biphenyl]-4-ol ))): PLC-16.1 (0.205 mmol, 181 mg), (4- Hydroxyphenyl)boronic acid (1.228 mmol, 169 mg), _K2CO3 (1.228 mmol, 170 mg), and Pd(dppf) _Cl2 (0.0512 mmol, 37.4 mg) in a microwave synthesizer at 110 ° _C . Synthesized within. The crude reaction mixture was loaded onto approximately 65 g of flash silica in a loader. Purified by silica gel flash chromatography (220 g, solids, no equilibration, elution 100% toluene (2 CV) → 10% EtOAc/toluene (20 CV)). Fractions containing product were evaporated to dryness in vacuo. 117 mg (61% yield) of a dark reddish-purple solid was obtained. MS (APCI): Calculated value (M-) for formula C ₅₉ H ₄₉ BCl ₂ F ₂ N ₂ O ₂ = 936; found value: 936. ¹ H NMR (400 MHz, tetrachloroethane-d ₂ ) δ 8.08-8.03 (m, 4H), 7.71-7.66 (m, 4H), 7.62-7.57 (m, 4H) ), 6.94 (d, J = 7.2Hz, 12H), 6.57 (s, 2H), 6.51 (d, J = 1.3Hz, 1H), 6.49 (s, 1H), 6.41 (dd, J=9.0, 7.0Hz, 1H), 5.03 (s, 2H), 1.19 (s, 18H).

Compound PLC-16 ((1,9-bis(4-(tert-butyl)phenyl)-10-(2,6-dichlorophenyl)-5,5-difluoro-5H-4l4,5l4-dipyrrolo[1,2- c:2',1'-f][1,3,2]diazaborinine-3,7-diyl)bis([1,1'-biphenyl]-4',4-diyl)bis(4-(4- (9-(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xanteno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)butanoate): Compound PLC-16 was added to PLC-16.2 (0.030 mmol, 28.1 mg), 4-(4-(9-(3,5-bis(trifluoromethyl)phenyl)-) in the same manner as above. 1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)butanoic acid (PLC-6.5) (0.090 mmol, 57 mg), DMAP pTsOH salt (0.120 mmol, 35.3 mg) and EDC·HCl (0.120 mmol, 23 mg). The crude reaction mixture was diluted with hexane and loaded onto approximately 30 g of flash silica in a loader. Silica gel flash chromatography (80 g, equilibration 100% hexane/0.5% EtOAc modifier, elution 100% hexane/0.5% EtOAc modifier (2 CV) → 100% DCM/0.5% EtOAc modifier agent (0 CV) → isocratic 100% DCM/0.5% EtOAc modifier (10 CV) → 100% DCM/1% EtOAc modifier (20 CV) → 100% DCM/2% EtOAc modifier (30 CV) )). Fractions containing product were evaporated to dryness in vacuo. The crude product was triturated with hot methanol. The product was dried in a vacuum oven at about 110°C. 47.6 mg (73% yield) of a dark red solid was obtained. ¹ H NMR (400 MHz, tetrachloroethane-d ₂ ) δ 8.65 (d, J = 7.8 Hz, 2H), 8.59 (d, J = 8.3 Hz, 2H), 8.24 (d, J =2.2Hz, 2H), 8.14 to 8.04 (m, 10H), 7.95 (s, 2H), 7.80 (dd, J = 8.6, 2.1Hz, 2H), 7 .77 to 7.69 (m, 8H), 7.65 (d, J = 8.3Hz, 4H), 7.56 (d, J = 8.6Hz, 2H), 7.37 (dd, J = 8.3, 5.6Hz, 6H), 7.30-7.24 (m, 4H), 6.95 (s, 8H), 6.59 (s, 2H), 6.54-6.48 ( m, 2H), 6.42 (dd, J=9.0, 7.0Hz, 1H), 4.04 (s, 4H), 1.19 (s, 18H).

Synthesis of compound PLC-17:

Compound PLC-17.1: 2-[4-(9-bromo-1,3-dioxo-1H-xanteno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid: DMF( A mixture of compound PLC-6.3 (400.0 mg, 1.1 mmol), 4-aminophenyl acetic acid (329.4 mg, 2.2 mmol) and DMAP (9.3 mg, 0.080 mmol) in 8 mL) was added at room temperature. I deflated. The mixture was then heated to 165°C and held at this temperature for 3 hours. TLC and LCMS showed about 95% conversion with no observable side reactions. The mixture was cooled to 50°C. It was then poured into acetone solution (40 mL), which was pre-cooled by a water-ice bath. The mixture was kept at 0° C. for 2 hours and then continued to stir at room temperature overnight. The solid was collected by vacuum filtration and washed with acetone (4 mL). It was then dried in a vacuum oven at 100° C. for 3 hours to obtain the pure compound as a tan solid (395.0 mg, 73% yield). MS (APCI): Calculated value ([M+H] ⁺ ) for formula C ₂₆ H ₁₄ BrNO ₅ = 500; found value: 500. ^1H NMR (400MHz, _CDCl2CDCl2 ) δ 8.65 (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) ).

Compound PLC-17.2: 2-[4-(1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinoline-2(3H) -yl)phenyl)acetic acid: A 100 mL vial was equipped with a stirring bar. In a vial, compound PLC-17.1 (400.0 mg, 0.80 mmol) in THF/DMF/H ₂ O (22 ml/4.4 ml/2.2 ml), 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. The reaction mixture was heated to 80°C and the reaction was kept at this temperature overnight. The reaction was monitored using TLC. After completion, the reaction was worked up by addition of 0.1N HCl (150ml) and EtOAc (150ml). The aqueous phase was further extracted with THF (150ml x 3). The combined organic phases were dried _over anhydrous Na ₂ SO , concentrated under a rotary evaporator and purified by flash chromatography using DCM in EtOAc (0% → 40%, containing 0.1% TFA) as eluent. Purification gave the pure RL-naphthalimide derivative as a yellow/tan solid (363.0 mg, 80% yield). MS (APCI): Calculated value for formula C ₃₃ H ₁₈ F ₃ NO ₅ ([M+H] ⁺ ) = 566; found 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) ).

Compound PLC-17: (1,9-bis(4-(tert-butyl)phenyl)-5,5-difluoro-10-mesityl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1 '-f][1,3,2]diazaborinine-3,7-diyl)bis([1,1'-biphenyl]-4',4-diyl)bis(2-(4-(1,3-dioxo -9-(trifluoromethyl)-1H-xanteno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate)): Compound PLC-17 was converted into compound PLC-17.2 (0.025 mmol, 22.8 mg), compound PLC-15.6 (0.075 mmol, 37 mg), DMAP pTsOH salt (0.100 mmol, 29 mg) and EDC HCl (0.125 mmol, 24 mg) ) was synthesized from The crude reaction mixture was diluted with hexane and loaded onto approximately 30 g of flash silica gel in a loader. Silica gel flash chromatography (80 g, solids, equilibration 100% hexane, elution 100% hexane (2 CV) → 100% DCM (0 CV) → 100% DCM (5 CV) → 100% DCM/1% EtOAc modifier (compound ) until elution. Fractions containing product were evaporated to dryness in vacuo. The product was triturated with hot methanol. The product was dried in a vacuum oven at about 110°C. 42 mg (91% yield) of a dark red solid was obtained. MS (APCI): Calculated value (M-) for formula C ₁₁₆ H ₈₁ BF ₈ N ₄ O ₁₀ = 1853; Found value: 1853. ¹ H NMR (400 MHz, tetrachloroethane-d ₂ ) δ 8.54 (d, J = 7.8 Hz, 2H), 8.51 (d, J = 8.3 Hz, 2H), 8.21 (d, J = 2.1Hz, 2H), 7.98 (d, J = 8.2Hz, 4H), 7.91 (d, J = 8.1Hz, 2H), 7.71 (dd, J = 8.9, 2.0Hz, 2H), 7.67 to 7.59 (m, 8H), 7.59 to 7.52 (m, 4H), 7.41 (d, J = 8.6Hz, 2H), 7. 31-7.24 (m, 6H), 7.21-7.14 (m, 4H), 6.83-6.76 (m, 4H), 6.61 (d, J = 8.3Hz, 4H ), 6.46 (s, 2H), 5.94 (s, 2H), 3.95 (s, 4H), 1.92 (s, 6H), 1.80 (s, 3H), 1.11 (s, 18H).

Synthesis of compound PLC-18:

Compound PLC-18.1 (2-[4-(9-(4-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)phenyl)-1,3-dioxo-1H-xantheno[2,1 ,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid): Compound PLC-18.1 was added to THF (60 mL), DMF (12 mL) and water (6 mL ) compound PLC-17.1 (2.00 mmol, 1001 mg), 2-(4-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)phenyl)-4,4,5,5-tetra from methyl-1,3,2-dioxaborolane (4.00 mmol, 1465 mg), K ₂ CO ₃ (5.50 mmol, 760 mg), and Pd(dppf)Cl ₂ (0.140 mmol, 102 mg) at 80° C. for 2 hours. It was synthesized over a period of time. The crude product reaction mixture was quenched with 6N HCl (5 mL) and diluted with water (50 mL) and THF (50 mL). Sodium chloride was added until the aqueous layer was saturated, then the layers were separated and the aqueous layer was extracted with THF (3 x 50 mL). The combined organic layers were washed with brine (50 mL), dried over _MgSO4 , filtered, and evaporated to dryness in vacuo (containing DMF). The crude product was evaporated onto approximately 50 g of flash silica gel and placed into a loader. Silica gel flash chromatography (220 g, solid content, equilibration 100% DCM, elution 100% DCM (2 CV) → 40% (EtOAc/0.1% TFA)/DCM (20 CV) → 70% (EtOAc/0.1%) TFA)/DCM (20CV)). Fractions containing product were evaporated to dryness in vacuo. 722 mg (55% yield) of a yellow solid was obtained. MS (APCI): Calculated for formula C ₃₉ H ₃₃ NO ₉ (M+H) = 660; Found: 660. ^1H NMR (400MHz, DMSO- _d6 ) δ 8.57 (d, J=2.2Hz, 1H), 8.52 (s, 2H), 8.48 (d, J=8.3Hz, 1H) , 7.90 (dd, J=8.7, 2.2Hz, 1H), 7.84-7.78 (m, 2H), 7.55 (d, J=8.7Hz, 1H), 7. 48 (d, J = 8.3Hz, 1H), 7.41 (d, J = 8.1Hz, 2H), 7.33-7.26 (m, 2H), 7.12-7.07 (m , 2H), 4.22-4.14 (m, 2H), 3.82-3.76 (m, 2H), 3.68 (s, 2H), 3.65-3.59 (m, 2H) ), 3.58-3.51 (m, 4H), 3.48-3.41 (m, 2H), 3.25 (s, 3H).

Compound PLC-18 ((5,5-difluoro-10-mesityl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-3,7 -diyl)bis([1,1'-biphenyl]-4',4-diyl)bis(2-(4-(9-(4-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy) phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate)): Compound PLC-18 was prepared as 4 ',4'''-(5,5-difluoro-10-mesityl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-3 ,7-diyl)bis([1,1'-biphenyl]-4-ol) (PLC-1.4, 0.040 mmol, 32 mg), compound PLC18.1 (0.120 mmol, 79.2 mg), DMAP. It was synthesized from pTsOH salt (0.160 mmol, 47.1 mg) and EDC·HCl (0.200 mmol, 38.3 mg). The crude product was loaded onto approximately 65 g of flash silica gel in a loader. Silica gel flash chromatography (120 g, solid content, equilibration 100% DCM, elution 100% DCM (2 CV) → 100% DCM/0.5% MeOH modifier (1 CV) → 100% DCM/1% MeOH modifier (1 CV) → 100% DCM/2% MeOH modifier (20 CV) → 100% DCM/3% MeOH modifier (5 CV)). The product elutes too slowly with 2% MeOH, but quickly with the 3% MeOH modifier. Fractions containing pure product were evaporated to dryness in vacuo. 40.8 mg (52.8% yield) of a dark red powder was obtained. MS (APCI): Calculated value (M-) for formula C ₁₂₀ H ₉₅ BF ₂ N ₄ O ₁₈ = 1929; Found value: 1929. ¹ H NMR (400 MHz, tetrachloroethane-d ₂ ) δ 8.61 (d, J = 7.8 Hz, 2H), 8.56 (d, J = 8.3 Hz, 2H), 8.18 (d, J = 2.2Hz, 2H), 8.08 (d, J = 8.2Hz, 4H), 8.00 (d, J = 8.2Hz, 2H), 7.79 to 7.68 (m, 10H) , 7.64 (t, J=8.5Hz, 8H), 7.46 (d, J=8.6Hz, 2H), 7.41 to 7.35 (m, 4H), 7.31 (d, J = 8.4Hz, 2H), 7.29 to 7.24 (m, 4H), 7.12 to 7.04 (m, 4H), 6.97 (t, J = 7.2Hz, 2H), 6.88 (t, J=7.5Hz, 4H), 6.80 (d, J=7.1Hz, 4H), 6.57 (s, 2H), 6.02 (s, 2H), 4. 22 (t, J = 4.8Hz, 4H), 4.04 (s, 4H), 3.90 (t, J = 4.8Hz, 4H), 3.78 to 3.72 (m, 4H), 3.72-3.62 (m, 8H), 3.59-3.53 (m, 4H), 3.38 (s, 6H), 2.02 (s, 6H), 1.87 (s, 3H).

Synthesis of compound PLC-19:

Compound PLC-19.1: ((E)-1-(4-bromophenyl)-3-(4-octylphenyl)prop-2-en-1-one): Compound PLC-19.1 was prepared as described above. Similar to the method, 1-(4-bromophenyl)ethane-1-one (22.9 mmol, 4.557 g), 4-octylbenzaldehyde (22.9 mmol, 5.00 g) in 200 proof EtOH (35 mL); and KOH (44.89 mmol, 2.519 g) at room temperature. The crude product was precipitated with water, filtered off, and recrystallized from 200 proof EtOH. 8.197 g (90% yield) of an off-white solid was obtained. MS (APCI): Calculated for formula _C23H27BrO (M+H) ₌ 399; Found: 399. ^1H NMR (400MHz, TCE) δ 7.91-7.85 (m, 2H), 7.79 (d, J = 15.6Hz, 1H), 7.70-7.64 (m, 2H), 7.61-7.55 (m, 2H), 7.44 (d, J = 15.7Hz, 1H), 7.29-7.23 (m, 2H), 2.70-2.60 (m , 2H), 1.66-1.61 (m, 2H), 1.39-1.20 (m, 10H), 0.92-0.86 (m, 3H).

Compound PLC-19.2 (1-(4-bromophenyl)-4-nitro-3-(4-octylphenyl)butan-1-one): Compound PLC-19.2 was prepared in the same manner as above. Synthesized from compound PLC-19.1 (20.52 mmol, 8.197 g) and KOH (4.104 mmol, 230 mg) in nitromethane (22 mL) and 200 proof ethanol (22 mL) at 95° C. for 1 hour. The crude reaction mixture was partitioned between 100 mL water and 100 mL EtOAc. A small amount of NaCl breaks the emulsion. The layers were separated and the organic layer was dried over _MgSO4 , filtered and evaporated to dryness in vacuo. 9.34 g (99% yield) of a dark brown oil was obtained. MS (APCI): Calculated for formula _C24H30BrNO3 ( _M +H) = ₄₆₀ ; Found: 460. ¹ H NMR (400MHz, TCE) δ 7.81-7.74 (m, 2H), 7.67-7.59 (m, 2H), 7.16 (s, 4H), 4.81 (dd, J=12.4, 6.6Hz, 1H), 4.67 (dd, J=12.5, 8.0Hz, 1H), 4.15 (p, J=6.8Hz, 1H), 3.43 (dd, J=17.9, 6.2Hz, 1H), 3.36 (dd, J=17.9, 7.5Hz, 1H), 2.62 to 2.51 (m, 2H), 1. 61-1.50 (m, 4H), 1.38-1.22 (m, 10H), 0.94-0.84 (m, 3H).

Compound PLC-19.3 (1-(4-bromophenyl)-4,4-dimethoxy-3-(4-octylphenyl)butan-1-one): Compound PLC-19.3 was prepared in the same manner as above. was synthesized from compound PLC-19.2 (20.29 mmol, 9.34 g) and KOH (52.54 mmol, 2.948 g) in dry THF (225 mL) and dry MeOH (115 mL). This solution was added dropwise to a solution of 95% H ₂ SO ₄ (25 mL) in dry MeOH (120 mL) at 0°C. After work-up and evaporation of all solvents in vacuo, 8.13 g (82% yield) of a brown oil was obtained. Mixture of dimethyl acetal and aldehyde. MS (APCI): Calculated for formula _C26H35BrO3 ( _M +H) = ₄₇₅ ; Found: 475.

Compound PLC-19.4 (2-(4-bromophenyl)-4-(4-octylphenyl)-1H-pyrrole): Compound PLC-19.4 was dissolved in AcOH (35 mL) similarly to the method described above. The compound PLC-19.3 (20.29 mmol, assumed to be 100% from the previous step) and NH ₄ OAc (109.4 mmol, 8.432 g) were synthesized at 100°C. After heating at 100° C. overnight, the reaction mixture was cooled to room temperature and water was added. The resulting precipitate was filtered off, dissolved in DCM, dried over MgSO ₄ and evaporated to dryness. The product was recrystallized from 200 proof ethanol. 3.652 g (41% yield) of a purple-blue solid was obtained. MS (APCI): Calculated for formula C ₂₄ H ₂₈ BrN (M+H) = 410; found: 410. ^1H NMR (400MHz, TCE) δ 8.49 (s, 1H), 7.56-7.50 (m, 2H), 7.50-7.44 (m, 2H), 7.43-7. 37 (m, 2H), 7.19 (d, J = 8.3Hz, 2H), 7.15 (t, J = 2.1Hz, 1H), 6.81 (dd, J = 2.6, 1 .6Hz, 1H), 2.66 to 2.56 (m, 2H), 1.70 to 1.56 (m, 4H), 1.42 to 1.21 (m, 8H), 0.94 to 0 .83 (m, 3H).

Compound PLC-19.5 (3,7-bis(4-bromophenyl)-5,5-difluoro-10-mesityl-1,9-bis(4-octylphenyl)-5H-4l4,5l4-dipyrrolo[1 , 2-c:2',1'-f][1,3,2]diazaborinine): Compound PLC-19.5 was prepared in a manner similar to the method described above to prepare compound PLC-19.5 in dry DCE (20 mL). 4 (2.10 mmol, 862 mg), 2,4,6-trimethylbenzaldehyde (1.00 mmol, 0.148 mL), and pTsOH.H ₂ O (0.400 mmol, 76 mg), then DDQ (1.700 mmol, 386 mg) and 2×Et ₃ N (8.00 mmol, 1.11 mL), and BF ₃ .OEt ₂ (12.00 mmol, 1.50 mL) at 60° C. and then at 50° C. The crude reaction mixture was diluted with hexane (~250 mL) and washed with 6N HCL (50 mL), water (50 mL), saturated _NaHCO3 (2 x 100 mL), and brine (50 mL). The organic layer was dried with _MgSO4 , filtered and evaporated to dryness in vacuo. The crude material was dissolved in hexane and loaded onto 65 g of silica gel in a loader. Purified by flash chromatography on silica gel (220 g, solids, equilibrated in 100% hexanes, elution 100% hexanes (2 CV) → 30% EtOAc/hexanes (30 CV)). Fractions containing product were evaporated to dryness in vacuo. 512 mg (51% yield) of a deep red solid was obtained. MS (APCI): Calculated for formula C ₅₈ H ₆₃ BBr ₂ F ₂ N ₂ (M+H) = 995; Found: 995. ^1H NMR (400MHz, TCE) δ 7.83-7.76 (m, 4H), 7.66-7.57 (m, 4H), 6.68 (d, J = 8.2Hz, 4H), 6.64 (d, J=8.1Hz, 4H), 6.43 (s, 2H), 6.04 (s, 2H), 2.46-2.35 (m, 4H), 1.97 ( s, 6H), 1.89 (s, 3H), 1.44 (p, J=6.8Hz, 4H), 1.38 to 1.21 (m, 22H), 0.95 to 0.86 ( m, 6H).

Compound PLC-19.6 (4',4'''-(5,5-difluoro-10-mesityl-1,9-bis(4-octylphenyl)-5H-4l4,5l4-dipyrrolo[1,2- c:2',1'-f][1,3,2]diazaborinine-3,7-diyl)bis([1,1'-biphenyl]-4-ol)): Compound PLC-19.6, Similar to the method described above, compound PLC-19.5 (0.200 mmol, 200 mg), 4-(4,4,5,5-tetramethyl-1,3, 2-dioxaborolan-2-yl)phenol (0.800 mmol, 176 mg), K ₂ CO ₃ (4.60 mmol, 636 mg), and Pd(dppf)Cl ₂ (0.020 mmol, 15 mg) in a microwave synthesizer. Synthesis was carried out at 110° C. for 3 hours. THF and water were evaporated in vacuo and the reaction mixture was dissolved in DCM and loaded onto approximately 40 g of silica gel in a loader. Purified by silica gel flash chromatography (220 g, solids, equilibrated 0% EtOAc/hexanes, elution 0% (2 CV) → 5% EtOAC/hexanes (30 CV)). Fractions containing product were evaporated to dryness in vacuo. 99 mg (48% yield) of a dark red solid was obtained. MS (APCI): Calculated for formula C ₇₀ H ₇₃ BF ₂ N ₂ O ₂ (M+H) = 1023; Found: 1023. ¹ H NMR (400MHz, TCE) δ 8.08-7.98 (m, 4H), 7.71-7.62 (m, 4H), 7.62-7.54 (m, 4H), 6. 98-6.89 (m, 4H), 6.73-6.64 (m, 8H), 6.52 (s, 2H), 6.05 (s, 2H), 4.98 (s, 2H) , 2.41 (dd, J=8.8, 6.7Hz, 4H), 2.00 (s, 6H), 1.90 (s, 3H), 1.53 to 1.39 (m, 4H) , 1.38-1.26 (m, 20H), 0.96-0.87 (m, 6H).

Compound PLC-19: ((5,5-difluoro-10-mesityl-1,9-bis(4-octylphenyl)-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f ][1,3,2]diazaborinine-3,7-diyl)bis([1,1'-biphenyl]-4',4-diyl)bis(2-(4-(1,3-dioxo-9- (4-(trifluoromethyl)phenyl)-1H-xanteno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate)): Compound 42 was prepared in the same manner as compound 36. Compound 42.1 (0.0400 mmol, 41 mg), compound 36.4 (0.120 mmol, 68 mg), and DMAP pTsOH salt (0.05 mg) were combined in a 40 mL screw cap vial containing a stir bar and dry DCM (10 mL). 160 mmol, 47 mg) and EDC·HCl (0.240 mmol, 46 mg). The crude product was loaded onto approximately 20 g of silica gel in a loader. Purified by silica gel flash chromatography (120 g, solid, equilibrated 0% EtOAc/DCM, elution 0% (2 CV) → 10% EtOAc/DCM (30 CV)). Fractions containing product were evaporated to dryness in vacuo. 52 mg (61% yield) of a deep red solid was obtained. ¹ H NMR (400 MHz, TCE) δ 8.63 (d, J = 7.8 Hz, 2H), 8.58 (d, J = 8.3 Hz, 2H), 8.23 (d, J = 2.3 Hz) , 2H), 8.07 (d, J = 8.2Hz, 4H), 8.02 (d, J = 8.1Hz, 2H), 7.83 to 7.75 (m, 10H), 7.75 ~7.69 (m, 8H), 7.65 (d, J = 8.4Hz, 4H), 7.52 (d, J = 8.6Hz, 2H), 7.41 ~ 7.36 (m, 4H), 7.34 (d, J = 8.3Hz, 2H), 7.26 (d, J = 8.6Hz, 4H), 6.75 to 6.63 (m, 8H), 6.54 ( s, 2H), 6.05 (s, 2H), 4.04 (s, 4H), 2.42 (t, J=7.7Hz, 4H), 2.01 (s, 6H), 1.91 (s, 3H), 1.51-1.39 (m, 4H), 1.37-1.25 (m, 20H), 0.95-0.88 (m, 6H).

Synthesis of compound PLC-20

Compound PLC-20.1: (4',4'''-(5,5-difluoro-10-mesityl-1,9-bis(4-octylphenyl)-5H-4l4,5l4-dipyrrolo[1,2 -c:2',1'-f][1,3,2]diazaborinine-3,7-diyl)bis([1,1'-biphenyl]-3-ol)): Compound PLC-20.1 , similar to the method described above, compound PLC-19.5 (0.200 mmol, 200 mg), (3-hydroxyphenyl)boronic acid (0.800 mmol, 110 mg), K in THF (10 mL) and water (2 mL). Synthesized from _{2CO 3} (4.60 mmol, 636 mg) and Pd(dppf)Cl ₂ (0.020 mmol, 15 mg) at 110° C. for 3 hours in a microwave synthesizer. THF and water were evaporated in vacuo and the reaction mixture was dissolved in DCM and loaded onto approximately 40 g of silica gel in a loader. Purified by silica gel flash chromatography (220 g, solid, equilibrated 0% EtOAc/hexanes, elution 0% (2 CV) → 5% EtOAC/hexanes (30 CV)). Fractions containing product were evaporated to dryness in vacuo. 101 mg (49% yield) of a dark red solid was obtained. MS (APCI): Calculated for formula C ₇₀ H ₇₃ BF ₂ N ₂ O ₂ (M+H) = 1023; Found: 1023. ^1H NMR (400MHz, TCE) δ 7.95 (d, J = 8.3Hz, 4H), 7.66-7.54 (m, 4H), 7.26 (t, J = 7.9Hz, 2H ), 7.17 (dt, J=7.9, 1.2 Hz, 2H), 7.05 (t, J=2.0 Hz, 2H), 6.76 (ddd, J=8.0, 2. 6, 1.0Hz, 2H), 6.64-6.54 (m, 8H), 6.44 (s, 2H), 5.96 (s, 2H), 4.86 (s, 2H), 2 .32 (t, J = 7.8Hz, 4H), 1.43 to 1.29 (m, 4H), 1.19 (d, J = 16.2Hz, 20H), 0.87 to 0.78 ( m, 6H).

Compound PLC-20: ((5,5-difluoro-10-mesityl-1,9-bis(4-octylphenyl)-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f ][1,3,2]diazaborinine-3,7-diyl)bis([1,1'-biphenyl]-4',3-diyl)bis(2-(4-(1,3-dioxo-9- (4-(trifluoromethyl)phenyl)-1H-xanteno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate)): Compound PLC-20 was prepared in the same manner as described above. , compound PLC20.1 (0.0400 mmol, 41 mg), compound PLC-17.2 (0.140 mmol, 79 mg), DMAP pTsOH salt, combined in a 40 mL screw cap vial containing a stir bar and dry DCM (10 mL). (0.160 mmol, 47 mg) and EDC·HCl (0.240 mmol, 46 mg). The crude product was loaded onto approximately 40 g of silica gel in a loader. Purified by silica gel flash chromatography (220 g, solids, equilibrated 0% EtOAc/DCM, elution 0% (2 CV) → 10% EtOAc/DCM (30 CV)). Fractions containing product were evaporated to dryness in vacuo. 47 mg (55% yield) of a deep red solid was obtained. ¹ H NMR (400 MHz, TCE) δ 8.61 (d, J = 7.9 Hz, 2H), 8.57 (d, J = 8.3 Hz, 2H), 8.21 (d, J = 2.2 Hz) , 2H), 8.08 (d, J = 8.2Hz, 4H), 8.00 (d, J = 8.2Hz, 2H), 7.82 to 7.72 (m, 14H), 7.63 (d, J=8.3Hz, 4H), 7.59 (d, J=7.9Hz, 2H), 7.52 to 7.44 (m, 6H), 7.40 to 7.35 (m, 4H), 7.33 (d, J = 8.3Hz, 2H), 7.14 (ddd, J = 8.0, 2.3, 1.0Hz, 2H), 6.74 to 6.63 (m , 8H), 6.54 (s, 2H), 6.05 (s, 2H), 4.04 (s, 4H), 2.41 (t, J = 7.8Hz, 4H), 2.00 ( s, 6H), 1.90 (s, 3H), 1.53 to 1.39 (m, 4H), 1.37 to 1.26 (m, 20H), 0.91 (t, J=6. 7Hz, 6H).

Synthesis of compound PLC-21:

Compound PLC-21.1: 2-[4-[9-(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinoline-2 (3H)-yl)phenyl)acetic acid: A 100 mL vial was equipped with a stirring bar. Compound PLC-17.1 (400.0 mg, 0.80 mmol) in THF/DMF/H ₂ O (22 ml/4.4 ml/2.2 ml) in a vial, 3,5-bis(trifluoromethyl)phenylboron Acid (262.2 mg, 1.6 mmol), Pd(dppf) _Cl2 (41.0 mg, 0.056 mmol) and _K2CO3 ( _412.6 mg, 2.2 mmol) were degassed at room temperature. The reaction mixture was heated to 80° C. and the reaction was kept at this temperature overnight. The reaction was monitored using TLC. After completion, the reaction was worked up by addition of 0.1N HCl (150ml) and EtOAc (150ml). The aqueous phase was further extracted with THF (150ml x 3). The combined organic phases were dried over anhydrous _{Na 2} SO , concentrated under a rotary evaporator and purified by flash chromatography using DCM in EtOAc (0% → 40%, containing 0.1% TFA) as eluent. Purified and pure RL-naphthalimide derivative PLC-21.1 was obtained as a yellow/tan solid (311.0 mg, 61% yield). MS (APCI): Calculated value for formula C ₃₄ H ₁₇ F ₆ NO ₅ ([M+H] ⁺ ) = 634; Found value: 634. ^1H NMR (400MHz, DMSO-d6) 8.73 (m, 1H), 8.46 (m, 5H), 8.10 (m, 2H), 7.57 (m, 1H), 7.42 ( d, J=8.0Hz, 2H), 7.40 (m, 1H), 7.30 (d, J=8.0Hz, 2H), 3.72 (s, 2H).

Compound PLC-21: A 25 mL vial was equipped with a stirring bar. In a vial, compound PLC-1.4 (40.0 mg, 0.05 mmol), compound PLC-21.1 (158.4 mg, 0.25 mmol), EDC・HCl (76.7 mg, 0.40 mmol) and DMAP・TsOH (75.0 mg, 0.25 mmol) was added followed by anhydrous DCM (4 ml). The reaction mixture was kept at room temperature for 48 hours. After the reaction was completed, the mixture was loaded on silica gel and purified by flash chromatography using DCM in EtOAc (0%→4%) as eluent to yield pure RL-naphthalimide-BODIPY compound PLC-21 as a dark purple solid. provided as. The solid was further triturated with EtOAc (1 mL) and MeOH (20 ml) to give RL-naphthalimide-BODIPY 1605-108 (60.0 mg, 60% yield). MS (APCI): Could not be observed with our LCMS system. ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) 8.65 (d, J = 8.0 Hz, 2H), 8.59 (d, J = 8.0 Hz, 2H), 8.24 (d, J = 2 .4Hz, 2H), 8.08 (m, 10H), 7.95 (s, 2H), 7.80 (dd, J=8.0Hz, 2.4Hz, 2H), 7.73 (m, 8H) ), 7.65 (m, 4H), 7.56 (d, J=8.0Hz, 2H), 7.38 (m, 6H), 7.26 (m, 4H), 6.97 (m, 2H), 6.88 (t, J=8.0Hz, 4H), 6.79 (m, 4H), 6.57 (s, 2H), 6.02 (s, 2H), 4.04 (s , 4H), 2.01 (s, 6H), 1.87 (s, 3H).

Synthesis of compound PLC-22:

Compound PLC-22.1: (9-bromo-2-(5-hydroxypentyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione). Compound PLC-6.3 (1.223 g, 3.33 mmol, 1 eq.) was suspended in 35 mL of anhydrous DMSO and 5-amino-1-pentanol (1.5 g, 20.0 mmol, 6 eq.) was added at room temperature. Added to reaction mixture. The resulting mixture was stirred at 160° C. for 45 minutes and LMCMS showed the reaction was complete. After cooling to room temperature, the solid product was filtered, washed with water (250 mL), then MeOH (100 mL), and dried in a vacuum oven to give 1.2 g of a greenish yellow solid (85% yield). I got it. MS ₍ APCI): Calcd for _C23H18BrNO4 ( _M- ) = 453; Found: 453. MS (APCI): Calculated value (M-) for formula C ₂₃ H ₁₈ BrNO ₄ = 452. ; Actual value: 452. ¹ H NMR (400 MHz) δ 8.52 (d, J = 7.8 Hz, 1 H), 8.48 (d, J = 8.3 Hz, 1 H), 8.09 (d, J = 2.3 Hz, 1 H ), 7.82 (d, J = 8.0 Hz, 1H), 7.54 (dd, J = 8.8, 2.3 Hz, 1H), 7.23 (d, J = 8.3 Hz, 1H) , 7.19 (d, J = 8.8 Hz, 1H), 4.14 to 4.02 (m, 2H), 3.64 to 3.49 (m, 2H), 1.68 (p, J = 7.7Hz, 2H), 1.60 to 1.54 (m, 2H), 1.41 (q, J=8.0Hz, 2H), 1.28 (s, 1H).

Compound PLC-22.2: (2-(5-hydroxypentyl)-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H) -dione): Compound PLC-22.1 (1.13 g, 2.5 mmol, 1 eq.) was suspended in DMF (10 ml), H ₂ O (5 ml), and 4-(trifluoromethyl)benzeneboronic acid ( 0.949g, 5.0mmol, 2eq), _K2CO3 ( _0.691g , 5.0mmol, 2eq), Pd(dppf) _Cl2.DCM (40.8mg, 0.05mmol, 0.02eq) ) was added. The mixture was degassed by three cycles of Vac-Fill argon and heated and stirred at 90° C. for 5 hours. The reaction mixture was cooled to room temperature and water was added. The resulting mixture was kept at room temperature for 12 hours. The greenish yellow solid was filtered and washed with water, then MeOH to give 1.24 g of a greenish yellow solid (95% yield). MS (APCI): Calculated value (M-) for formula C ₃₀ H ₂₂ F ₃ NO ₄ = 517; Found value: 517. ^1H NMR (400MHz) δ 8.56 (d, J = 7.9Hz, 1H), 8.51 (d, J = 8.3Hz, 1H), 8.17 (d, J = 2.1Hz, 1H ), 7.97 (d, J=8.0Hz, 1H), 7.69 (dd, J=10.3, 1.9Hz, 4H), 7.42 (d, J=8.6Hz, 1H) , 7.28 (d, J = 8.3 Hz, 1H), 4.09 (t, J = 7.5 Hz, 2H), 3.57 (q, J = 6.2 Hz, 2H), 1.69 ( p, J = 7.8Hz, 2H), 1.61 to 1.54 (m, 2H), 1.42 (q, J = 8.0Hz, 2H), 1.28 (t, J = 5.5Hz , 1H).

Compound PLC-22.3: (2-(5-bromopentyl)-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H) -dione): A mixture of PLC-22.2 (0.66 g, 1.288 mmol) and 48% aqueous HBr (20.0 ml) was refluxed (HBr 48% bp) in a heat block at 120 °C for 5 h with stirring. :126°C). After cooling to room temperature, the mixture was poured into ice water and the solid was filtered, washed with water and dried in a vacuum oven to yield 82% of the desired compound containing unreacted SM. Obtained 0.7 g of a greenish yellow solid (93% yield). The product was used in the next step without further purification. MS (APCI): Calculated value (M-) for formula C ₃₀ H ₂₁ BrF ₃ NO ₃ = 581; found value: 581. ^1H NMR (400MHz) δ 8.57 (d, J = 7.9Hz, 1H), 8.51 (d, J = 8.3Hz, 1H), 8.18 (d, J = 2.2Hz, 1H ), 7.98 (d, J=7.9Hz, 1H), 7.69 (dd, J=9.6, 2.0Hz, 4H), 7.43 (d, J=8.6Hz, 1H) , 7.28 (d, J = 8.3 Hz, 1H), 4.09 (t, J = 7.5 Hz, 3H), 3.38 (t, J = 6.7 Hz, 2H), 1.97 ~ 1.81 (m, 2H), 1.69 (t, J=7.8Hz, 2H).

Compound PLC-22: 2'-(5,5-difluoro-10-mesityl-1,9-diphenyl-5H-4l ⁴ ,5l ⁵ -dipyrrolo[1,2-c:2',1'-f][ 1,3,2]diazaborinine-3,7-diyl)bis([1,1'-biphenyl]-4',4-diyl))bis(oxy))bis(pentane-5,1-diyl))bis (9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione). Compound 22.3 (7.625 mg, 0.15 mmol, 3 eq.) was suspended in anhydrous DCM (10.0 ml), compound 1.4 (39.93 mg, 0.05 mmol, 1 eq.), K ₂ CO ₃ ( 20.73 mg, 0.15 mmol, 3 eq.) was added and the mixture was stirred at 65° C. for 45 minutes under an argon atmosphere. The mixture was concentrated to dryness, the solid was washed with 50 ml of water, dissolved in DCM and loaded onto an ₈₀ g SiO column, Hex-DCM (1/1), DCM only, then 0.5% in DCM. Elution with EA and washing with MeOH gave 82 mg, 94% yield. ¹ H NMR (400MHz) δ 8.50 (d, J = 7.9Hz, 2H), 8.45 (d, J = 8.3Hz, 2H), 8.10 (d, J = 2.1Hz, 2H ), 7.94 (d, J = 8.2 Hz, 4H), 7.90 (d, J = 8.1 Hz, 2H), 7.68 (s, 7H), 7.65 (dd, J = 8 .6, 2.2Hz, 2H), 7.58 (d, J=8.4Hz, 4H), 7.50 (d, J=8.7Hz, 4H), 7.37 (d, J=8. 6Hz, 2H), 7.21 (d, J = 8.3Hz, 2H), 6.88 (t, J = 8.0Hz, 6H), 6.79 (t, J = 7.5Hz, 4H), 6.69 (d, J=7.1Hz, 4H), 6.46 (s, 2H), 4.11 (t, J=7.4Hz, 4H), 3.95 (t, J=6.4Hz , 4H), 1.91 (s, 6H), 1.88-1.68 (m, 11H).

Example 3: Preparation of Color Conversion Film A glass substrate was prepared essentially as follows. A 1.1 mm thick glass substrate measuring 1 inch by 1 inch was cut to size. The glass substrates were then washed with detergent and deionized (DI) water, rinsed with fresh DI water, and sonicated for about 1 hour. The glass was then immersed in isopropanol (IPA) and sonicated for about 1 hour. Next, the glass substrate was immersed in acetone and subjected to ultrasonic treatment for about 1 hour. The glass was then removed from the acetone bath and dried with nitrogen gas at room temperature.

A 20% by weight solution of poly(methyl methacrylate) (PMMA) (average molecular weight by GPC 120,000, MilliporeSigma, Burlington, Mass., USA) copolymer in cyclopentanone (99.9% purity) was prepared. The prepared copolymer was stirred at 40° C. overnight. (PMMA) CAS: 9011-14-7, (cyclopentanone) CAS: 120-92-3.

The 20% PMMA solution (4 g) prepared above was added to 3 mg of the photoluminescent complex prepared above in a sealed container and mixed for about 30 minutes. Next, the PMMA/Lumiphor solution was spin-coated onto the prepared glass substrate at 1000 RPM for 20 seconds and then at 500 RPM for 5 seconds. The resulting wet coating had a thickness of approximately 10 μm. The samples were covered with aluminum foil before spin coating to protect the samples from light exposure. Three samples were made in this way, each for emission/FWHM and quantum yield. The spin-coated sample was baked in a vacuum oven at 80° C. for 3 hours to evaporate the remaining solvent.

A 1 inch by 1 inch sample was inserted into a Shimadzu Instruments UV-3600 UV-VIS-NIR spectrophotometer (Shimadzu Instruments, Inc., Columbia, MD, USA). All device operations were performed in a nitrogen-filled glovebox. The absorption/emission spectrum obtained for PLC-1 is shown in FIG. The absorption/emission spectrum of the obtained PLC-2 is shown in FIG. The absorption/emission spectrum of the obtained PLC-4 is shown in FIG. The absorption/emission spectrum of the obtained PLC-5 is shown in FIG.

Fluorescence spectra of 1 inch x 1 inch film samples prepared as described above were measured at their respective maximum absorbance wavelengths using a Fluorolog spectrofluorometer (Horiba Scientific, Edison, NJ, USA). It was determined using the set excitation wavelength. The maximum release and FWHM are shown in Table 1.

Quantum yields of 1 inch x 1 inch samples prepared as described above were excited at their respective maximum absorption wavelengths using a Quantarus-QY spectrophotometer (Hamamatsu Inc., Campbell, CA, USA). It was decided that The results are reported in Table 1.

The results of the film characterization (absorption peak wavelength, FWHM, and quantum yield) are shown in Table 1 below.

Claims (19)

A photoluminescent complex,
a blue light-absorbing xanthenoisoquinoline derivative;
a linker complex that is an unsubstituted ester or a substituted ester;
a boron-dipyrromethene (BODIPY) moiety;
including;
The linker complex covalently bonds the xanthenoisoquinoline derivative and the BODIPY moiety, and the photoluminescent complex absorbs light energy at a first excitation wavelength and emits light energy at a second higher wavelength. , a photoluminescent complex, wherein said photoluminescent complex has an emission quantum yield of greater than 80%. The xanthenoisoquinoline derivative has the general formula:

(wherein R ⁰ and R ¹⁰ are independently a hydrogen atom (H), a C ₁ -C ₄ alkyl group, or an optionally substituted aryl group), according to claim 1 photoluminescent complex. The BODIPY portion has the general formula:

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ are independently a hydrogen atom (H), a C ₁ to C ₃ alkyl group, an optionally substituted aryl group, or an ether is the basis,
R ⁷ , R ⁸ and R ⁹ are independently hydrogen (H), a methyl group (-CH ₃ ), or -Cl,
2. The photoluminescent complex of claim ₁ , wherein L1 and _L2 are the linker complex. 4. The photoluminescent complex of claim 3, wherein ^R3 and ^R4 contain optionally substituted aryl groups. The optionally substituted aryl group is phenyl, or

The photoluminescent complex according to claim 4, wherein R ¹¹ is C ₁ -C ₈ alkyl. The optionally substituted aryl group is

The photoluminescent complex according to claim 5. R ¹ and R ⁶ are

The photoluminescent complex according to claim 1, 2, 3, 4, 5, or 6, which is. The linker complex is

The photoluminescent complex according to claim 1. The linker complex is

The photoluminescent complex according to claim 1. The linker complex is

The photoluminescent complex according to claim 1, wherein n is 1, 2 or 3. The linker complex is

The photoluminescent complex according to claim 1, wherein n is 2, 3, 4 or 5. The linker complex is

The photoluminescent complex according to claim 1. The photoluminescent complex has the following structure:

or one of a combination thereof. A color conversion film,
a transparent base material layer;
a color conversion layer including a resin matrix;
the photoluminescent complex of claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, or 13 dispersed within the resin matrix;
Including color conversion film. 15. The color conversion film of claim 14, wherein the film has a thickness of about 10 μm to 200 μm. 15. The color conversion film of claim 14, wherein the film absorbs light in a wavelength range of about 400 nm to about 480 nm and emits light in a wavelength range of 575 nm to about 645 nm. A method for producing a color conversion film according to claim 14, 15 or 16, comprising:
dissolving the photoluminescent complex and the binder resin in a solvent;
applying the mixture to one of the opposing surfaces of the transparent substrate;
including methods. A backlight unit comprising the color conversion film according to claim 14, 15, or 16. A display device comprising a backlight unit according to claim 18.