JP2024511260A - Boron-containing cyclic releasing compound and color conversion film containing the same - Google Patents

Abstract

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

Description

[Cross reference to related applications]
This application has priority to U.S. Provisional Patent Application No. 63/152,309, filed on February 22, 2021, and U.S. Provisional Patent Application No. 63/278,904, filed on November 12, 2021. and are incorporated herein by reference in their 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 provide novel color converting dye complexes with good blue light absorption and narrow emission bandwidths, eg, 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 moiety, a linker complex that is a substituted ester, an unsubstituted ester, a substituted ether, or an unsubstituted ether, and a boron-dipyrromethene ( BODIPY) portion. In some embodiments, the blue light absorbing moiety is a xanthenoisoquinoline derivative. 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 blue light absorbing moiety is a naphthalimide derivative. In some embodiments, a linker complex can covalently attach a naphthalimide derivative to a BODIPY moiety. In some embodiments, the naphthalimide 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 naphthalimide 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、各Ｒ^０及びＲ^１０は、独立して、水素（Ｈ）、Ｃ_１～Ｃ_４アルキル基、トリフルオロメチル基、アルコキシ基、－（ＯＣＨ_２ＣＨ_２）_ｎ－ＯＣＨ_３（式中、ｎは、１、２、３、又は４である）、又は任意に置換されたアリール基である）。 In some embodiments, the xanthenoisoquinoline derivative can be of the following general formula:

(In the formula, each R ⁰ and R ¹⁰ are independently hydrogen (H), a C ₁ -C ₄ alkyl group, a trifluoromethyl group, an alkoxy group, -(OCH ₂ CH ₂ ) _n -OCH ₃ (Formula (in which n is 1, 2, 3, or 4) or an optionally substituted aryl group).

（式中、各Ｒ^０及びＲ^１０は、独立して、水素（Ｈ）、Ｃ_１～Ｃ_４アルキル基、トリフルオロメチル基、アルコキシ基、－（ＯＣＨ_２ＣＨ_２）_ｎ－ＯＣＨ_３（式中、ｎは、１、２、３、又は４である）、又は任意に置換されたアリール基である）。 In some embodiments, the naphthalimide derivative can be of the following general formula:

(In the formula, each R ⁰ and R ¹⁰ are independently hydrogen (H), a C ₁ -C ₄ alkyl group, a trifluoromethyl group, an alkoxy group, -(OCH ₂ CH ₂ ) _n -OCH ₃ (Formula (in which n is 1, 2, 3, or 4) or an optionally substituted aryl group).

であり得る。幾つかの実施の形態においては、Ｒ^１及びＲ^６は、独立して、水素（Ｈ）、アルキル基、又はアルケン基であり得る。幾つかの実施の形態においては、Ｒ^３及びＲ^４は、Ｃ_１～Ｃ_２アルキルであり得る。幾つかの実施の形態においては、Ｒ^２及びＲ^５は、水素（Ｈ）、アルキル、シアノ（－ＣＮ）、－Ｃ（＝Ｏ）－（ＯＣＨ_２ＣＨ_２）_ｎ－ＯＣＨ_３（式中、ｎは１、２、３、又は４である）、アルキルエステル、又はアリールエステルであり得る。幾つかの実施の形態においては、Ｒ^７及びＲ^８は、水素（Ｈ）、メチル基、ハロゲン化物、又はＣ_１～Ｃ_３アルコキシ基であり得る。 In some embodiments, the BODIPY moiety has the following general formula:

It can be. In some embodiments, R ¹ and R ⁶ can independently be hydrogen (H), an alkyl group, or an alkene group. In some embodiments, R ³ and R ⁴ can be C ₁ -C ₂ alkyl. In some embodiments, R ² and R ⁵ are hydrogen (H), alkyl, cyano (-CN), -C(=O)-(OCH ₂ CH ₂ ) _n -OCH ₃ , where n is 1, 2, 3, or 4), an alkyl ester, or an aryl ester. In some embodiments, R ⁷ and R ⁸ can be hydrogen (H), methyl, halide, or C ₁ -C ₃ alkoxy.

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 a photoluminescent complex described herein dispersed within the resin matrix. In some embodiments, the color conversion film can have a thickness between 1 μm and about 200 μm. In some embodiments, the color conversion film of the present disclosure can absorb blue light in the range of 400 nm to about 480 nm and emit light in the wavelength range of 500 nm to about 560 nm. Another embodiment includes a color conversion film that can absorb blue light in the range of 400 nm to about 480 nm and emit light in the wavelength range of 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.

In some embodiments, the color conversion film of the present disclosure can include a singlet oxygen quencher. In some embodiments, the color conversion film can further include a free radical scavenger.

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

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 an absorption spectrum of one embodiment of a photoluminescent complex (PLC-1). 1 is a graph showing the emission spectrum 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).

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

This disclosure describes 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 includes 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. A substituted group is derived from an unsubstituted parent structure, wherein one or more hydrogen atoms on the parent structure are independently replaced by one or more substituents. In one or more forms, the substituents 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 constituent carbon atoms are replaced by nitrogen, oxygen, or sulfur. 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. Furthermore, up to two heteroatoms may be consecutive, such as -CH ₂ -NH-O-CH ₃ and the like.

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) 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.

等が挙げられる。多環式基の実例としては、以下の部分：

が挙げられる。 The term "hydrocarbon ring" refers to a monocyclic or polycyclic ring or ring system containing only carbon and hydrogen, and may be saturated. Monocyclic hydrocarbon rings include groups having from 3 to 12 carbon atoms. Examples of monocyclic groups include:

etc. Examples of polycyclic groups include:

can be mentioned.

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 group substituted with aryl. Non-limiting aralkyl groups include benzyl, phenethyl, and the like.

The term "heteroaryl" refers to an aryl group containing one or more ring heteroatoms selected from nitrogen, oxygen, and sulfur, and a heteroaryl group has from 4 to 10 atoms in its ring system. It is understood that heteroaryl rings can have additional heteroatoms within the ring. In a heteroaryl having two or more heteroatoms, the two or more heteroatoms may be the same or different from each other. Heteroaryls can be optionally substituted. An N-containing heteroaryl moiety refers to an aryl group in which the backbone atoms of the ring are nitrogen atoms. Illustrative examples of heteroaryl groups include the following moieties: pyrrole, imidazole, 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 "cyano" or "nitrile" as used herein refers to any organic compound containing the -CN functionality.

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). (including formula parts). Any hydroxy or carboxyl side chains on the compounds described herein may be esterified. Any suitable procedure and specific group for making such esters can be utilized.

As used herein, the term "ether" refers to two alkyl groups having the general formula R-O-R', where R and R' are alkyl and/or aryl. or refers to a chemical moiety containing an oxygen atom attached to an aryl group. Similarly, the term "alkoxy" refers to a chemical moiety containing an oxygen atom attached to an alkyl group that is further attached to an alkyl or aryl group.

As used herein, the term "ketone" refers to two alkyl groups having the general formula RC(=O)R', where R and R' are alkyl and/or aryl. or refers to a chemical moiety containing a carbonyl group (carbon-oxygen double bond) connected to an aryl group.

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 disubstituted boron atom, typically dipyrromethene complexed with _BF2 units. The IUPAC name for the BODIPY core (ie, without any substituents) 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" refers to the formula:

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

を有する化学部分を指す。 As used herein, the term "naphthalimide" or "naphthalimide derivative" refers to the formula:

Refers to a chemical moiety with

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 adjusted such that the absorbing emissive moiety transfers its energy to the acceptor emissive moiety, and the acceptor emits light. The portion then emits at a second wavelength that is greater than the first wavelength at which it was absorbed.

In some embodiments, the photoluminescent complex includes a blue light absorbing moiety, a linker complex, and a boron-dipyromethene (BODIPY) moiety. In some embodiments, the blue light absorbing moiety is a xanthenoisoquinoline derivative. 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 a first excitation wavelength and transfers energy to the BODIPY moiety, which then emits light energy at a second wavelength. Here, the optical energy of the second wavelength is higher than that of the first wavelength.

In some embodiments, the blue light absorbing moiety is a naphthalimide derivative. In some embodiments, a linker complex can covalently attach a naphthalimide derivative to a BODIPY moiety. In some embodiments, the naphthalimide derivative absorbs light at a first excitation wavelength and transfers energy to the BODIPY moiety, which then emits light energy at a second wavelength. Here, the optical energy of the second wavelength is higher than that of the first wavelength.

Energy transfer from the excited xanthenoisoquinoline derivative or naphthalimide 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 or naphthalimide derivatives) and the other in the BODIPY absorption band. There is only one emission band in the emission wavelength of the BODIPY part (see Figures 1 and 2).

In some embodiments, photoluminescent complexes can have high emission quantum yields. In some embodiments, 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 that can have 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 less than or equal to about 35 nm, less than or equal to about 30 nm, less than or equal to about 25 nm, or less than or equal to about 20 nm.

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 substituting the BODIPY moiety with different substituents, the emission wavelength can be tuned between about 500 nm and about 560 nm, or any value limited by this range.

In some embodiments, the blue light absorbing moiety may have a peak absorption maximum between wavelengths of about 400 nm to about 470 nm. In some embodiments, the peak absorption 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 435 nm. to 440nm, about 440nm to 445nm, about 445nm to 450nm, about 450nm to 455nm, about 455nm to 460nm, about 460nm to 465nm, about 465nm to 470nm, or any within the range limited by any of these values. wavelength.

In some embodiments, the photoluminescent complex may have an emission peak between about 500 nm and about 560 nm. In some embodiments, the emission peak is about 500 nm to about 515 nm, about 515 nm to about 520 nm, about 520 nm to about 525 nm, about 525 nm to about 530 nm, about 530 nm to about 535 nm, about 535 nm to about 540 nm, about 540 nm. to about 545 nm, about 545 nm to about 550 nm, about 550 nm to about 555 nm, about 555 nm to about 560 nm, or any wavelength within the range limited by any of these ranges.

Some embodiments include a photoluminescent complex in which the spatial distance between the blue light absorbing xanthenoisoquinoline or derivative and the BODIPY moiety is such that for transfer of energy of the blue light absorbing xantenoisoquinoline derivative to the BODIPY moiety, Regulated via a linker complex.

Other embodiments include a Linker complex through a linker complex to move the energy of the blue light -absorbing naphtalimide derivative and the BODIPY part, which includes the Photoni Nessen combination, and the energy of the blue light -absorbing naphtalimide derivative. It is adjusted accordingly.

The present disclosure includes a photoluminescent complex (PLC), which can 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 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. The photoluminescent complexes have an emission quantum yield of over 80%.

（式中、Ｒ^０及びＲ^１０は、水素（Ｈ）、Ｃ_１～Ｃ_４アルキル基（例えば、メチル、ｎ－ブチル、ｔ－ブチル等）、トリフルオロメチル基、任意に置換されたアリール基、－（ＯＣＨ_２ＣＨ_２）_ｎ－ＯＣＨ_３（式中、ｎは、１、２、３、又は４である）、又はアルコキシ基であり得る）のものであり得る。 Some embodiments include blue light absorbing xanthenoisoquinoline derivatives, wherein the blue light absorbing xanthenoisoquinoline derivatives have the following general formula:

(In the formula, R ⁰ and R ¹⁰ are hydrogen (H), a C ₁ -C ₄ alkyl group (for example, methyl, n-butyl, t-butyl, etc.), a trifluoromethyl group, an optionally substituted aryl group , -(OCH ₂ CH ₂ ) _n -OCH ₃ , where n is 1, 2, 3, or 4, or an alkoxy group).

In some embodiments, R ¹⁰ is C _1-4 alkyl, such as methyl, ethyl, n-propyl, isopropyl, butyl, t-butyl.

In some embodiments, R ¹⁰ is t-butyl.

であり得る。 In some embodiments, R ¹⁰ is unsubstituted phenyl,

It can be.

であり得る。幾つかの実施形態においては、Ｒ^１０は、

であり得る。幾つかの実施形態においては、Ｒ^１０は、

であり得る。幾つかの実施形態においては、Ｒ^１０は、

であり得る。幾つかの実施形態においては、Ｒ^１０は、

であり得る。幾つかの実施形態においては、Ｒ^１０は、

であり得る。幾つかの実施形態においては、Ｒ^１０は、

であり得る。幾つかの実施形態においては、Ｒ^１０は、

であり得る。 In some embodiments, R ¹⁰ can be unsubstituted phenyl. In some embodiments, R ¹⁰ is

It can be. In some embodiments, R ¹⁰ is

It can be. In some embodiments, R ¹⁰ is

It can be. In some embodiments, R ¹⁰ is

It can be. In some embodiments, R ¹⁰ is

It can be. In some embodiments, R ¹⁰ is

It can be. In some embodiments, R ¹⁰ is

It can be. In some embodiments, R ¹⁰ is

It can be.

を含む、アルコキシ部分を含み得る。 In some embodiments, R ¹⁰ is, but is not limited to, methoxy (-OMe), or

may contain alkoxy moieties, including.

であり得る。 In some embodiments, R ¹⁰ can be methoxy. In some embodiments, R ¹⁰ is

It can be.

Some embodiments include a photoluminescent complex (PLC), which can include a blue light absorbing naphthalimide derivative, a linker complex, and a BODIPY moiety. The linker complex covalently bonds the blue light absorbing naphthalimide derivative and the BODIPY moiety. In some embodiments, the naphthalimide derivative absorbs light energy at a first excitation wavelength and transfers the energy to a BODIPY moiety, and the BODIPY moiety absorbs energy from the naphthalimide derivative and transfers the energy to a second excitation wavelength. Emit light energy at high wavelengths. In such embodiments, the photoluminescent complex has an emission quantum yield of greater than 80%.

（式中、Ｒ^０及びＲ^１０は、キサンテノイソキノリン誘導体について上に定義されるとおりである）のものであり得る。 Some embodiments include blue light absorbing naphthalimide derivatives, where the blue light absorbing naphthalimide derivatives have the following general formula:

where R ⁰ and R ¹⁰ are as defined above for xanthenoisoquinoline derivatives.

The linker complex covalently attaches the blue-absorbing xantenoisoquinoline derivative (or naphthalimide derivative) to the BODIPY moiety. The linker complex can be tailored to adjust the spatial distance between the blue light absorbing xanthenoisoquinoline derivative (or naphthalimide derivative) and the BODIPY moiety. By adjusting the spatial distance between the xanthenoisoquinoline derivative (or naphthalimide derivative) and BODIPY, the quantum yield can be adjusted. In some embodiments, the distance separating the blue light absorbing xanthenoisoquinoline derivative (or naphthalimide derivative) and the BODIPY moiety can be about 8 Å or less. The linker complex can maintain the distance between the blue light absorbing xantenoisoquinoline derivative (or naphthalimide derivative) and the BODIPY moiety.

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

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

In some embodiments, the linker conjugate can include a substituted ester, an unsubstituted ester, a substituted ether, or an unsubstituted ether. In some embodiments, the linker conjugate can include an optionally substituted ester group.

を有し得る。 In some embodiments, the linker complex includes a substituted ester group, and the linker complex has the following structure:

may have.

を有し得る。 In some embodiments, the linker conjugate may include an unsubstituted ester group, and the linker conjugate has the following structure:

may have.

In some embodiments, the linker complex can be:

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

It can be.

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

It can be.

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

It can be.

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

It can be.

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

It can be.

In some embodiments, the linker complex can be -O(CH ₂ ) ₆ -.

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

It can be.

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

It can be.

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

It can be.

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

It can be.

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

It can be.

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

It can be.

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

It can be.

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

could be.

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

It can be.

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

It can be.

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

It can be.

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

It can be.

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

It can be.

In some embodiments, the linker complex can be -O(CH ₂ ) ₆ -.

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

It can be.

Photoluminescent complexes of the present disclosure can include a BODIPY moiety.

（式中、Ｒ^１及びＲ^６は、独立して、水素（Ｈ）、飽和若しくは不飽和アルキル基、例えばメチル基及び／又はアルケン基から選択することができ、
Ｒ^３及びＲ^４は、独立して、Ｃ_１～Ｃ_２アルキル、例えばメチル基から選択することができ、
Ｒ^２及びＲ^５は、独立して、水素（Ｈ）、飽和アルキル、不飽和アルキル、シアノ（－ＣＮ）、アルキルエステル（例えば、エチルエステル、２－エチル－ヘキシルエステル、２，２，２－トリフルオロエチルエステル、グリコールエステル）、又はアリールエステル（例えば、ベンジルエステル（－ＣＯＯＣＨ_２Ｐｈ））から選択することができ、
Ｒ^７及びＲ^８は、水素（Ｈ）、Ｃ_１～Ｃ_３アルキル（例えば、メチル（－ＣＨ_３））、ハロゲン化物（例えば、Ｆ又はＣｌ）、及び／又はＣ_１～Ｃ_３アルコキシ（例えば、メトキシ（－ＯＣＨ_３））から独立して選択することができ、
Ｌは、任意に置換されたエステル又は任意に置換されたエーテルリンカーを含むリンカー複合体を表すことができる）を有することができる。 The BODIPY part has the following general formula:

(wherein R ¹ and R ⁶ can be independently selected from hydrogen (H), saturated or unsaturated alkyl groups, such as methyl groups and/or alkene groups,
R ³ and R ⁴ may be independently selected from C ₁ -C ₂ alkyl, such as a methyl group;
R ² and R ⁵ are independently hydrogen (H), saturated alkyl, unsaturated alkyl, cyano (-CN), alkyl ester (e.g., ethyl ester, 2-ethyl-hexyl ester, 2,2,2- trifluoroethyl esters, glycol esters), or aryl esters (e.g. benzyl esters (-COOCH ₂ Ph));
R ⁷ and R ⁸ are hydrogen (H), C ₁ -C ₃ alkyl (e.g. methyl (-CH ₃ )), halide (e.g. F or Cl), and/or C ₁ -C ₃ alkoxy (e.g. , methoxy (-OCH ₃ ));
L can represent a linker complex comprising an optionally substituted ester or an optionally substituted ether linker).

In some embodiments, the BODIPY moieties of the present disclosure may be such that R ¹ , R ³ , R ⁴ and R ⁶ are each methyl, and R ² and R ⁵ are substituted ester groups; The group may be a BODIPY moiety comprising a C ₁ -C ₇ alkyl chain or a polyglycol chain, R ⁷ and R ⁸ are each methyl, and L comprises a linker complex.

であってもよい。 In some embodiments, R ² and R ⁵ are independently

It may be.

である。 In some embodiments, R ² is

It is.

である。 In some embodiments, R ² is

It is.

である。 In some embodiments, R ² is

It is.

である。 In some embodiments, R ² is

It is.

である。 In some embodiments, R ² is

It is.

である。 In some embodiments, R ⁵ is

It is.

である。 In some embodiments, R ⁵ is

It is.

である。 In some embodiments, R ⁵ is

It is.

である。 In some embodiments, R ⁵ is

It is.

である。 In some embodiments, R ⁵ is

It is.

The photoluminescent complexes of the present disclosure can be represented by the following, which is provided for illustrative purposes and is not to be construed as a limitation in any way:

Some embodiments include a photoluminescent complex that includes a blue light absorbing xanthenoisoquinoline derivative. Blue light absorbing xanthenoisoquinoline derivatives can include organic lumiphores. In some embodiments, the xanthenoisoquinoline derivative has a wavelength of 400 nm to about 480 nm, about 400 nm to about 410 nm, about 410 nm to about 420 nm, about 420 nm to about 430 nm, about 430 nm to about 440 nm, about 440 nm to about 450 nm, about It may have a maximum absorption at any wavelength of light within the range of 450 nm to about 460 nm, about 460 nm to about 470 nm, about 470 nm to about 480 nm, or a range limited by any of these values. In some embodiments, the photoluminescent complex may have an absorption maximum peak at about 450 nm. In other embodiments, the blue light absorbing xanthenoisoquinoline derivative may have a maximum peak absorption at about 405 nm. In yet other embodiments, the blue light absorbing xanthenoisoquinoline derivative may have a maximum peak absorption at about 480 nm.

Some embodiments include a photoluminescent complex that includes a blue light absorbing naphthalimide derivative. Blue light absorbing naphthalimide derivatives can include organic lumiphores. In some embodiments, the naphthalimide derivative has a wavelength of 400 nm to about 480 nm, about 400 nm to about 410 nm, about 410 nm to about 420 nm, about 420 nm to about 430 nm, about 430 nm to about 440 nm, about 440 nm to about 450 nm, about 450 nm. It may have a maximum absorption at any wavelength of light within the range of ˜about 460 nm, about 460 nm to about 470 nm, about 470 nm to about 480 nm, or a range limited by any of these values. In some embodiments, the photoluminescent complex may have an absorption maximum peak at about 450 nm. In other embodiments, the blue light absorbing naphthalimide derivative may have a maximum peak absorption at about 405 nm. In yet other embodiments, the blue light absorbing naphthalimide derivative may have a maximum peak absorption at about 480 nm.

Some embodiments include a color conversion film that includes a color conversion layer that includes a resin matrix and a photoluminescent complex as described above dispersed within the resin matrix. In some embodiments, the color conversion film may include one or more complexes described herein.

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 about 5 μm, about 5 μm to about 10 μm, about 10 μm to about 15 μm, about 15 μm to about 20 μm, about 20 μm to about 40 μm, about 40 μm to about 80 μm, about It has a thickness of 80 μm to about 120 μm, about 120 μm to about 160 μm, about 160 μm to about 200 μm, or any thickness within the range limited by any of the above values.

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 500 nm to about 560 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 a transparent substrate from those used in the art. 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 above can include a transparent substrate 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. A person skilled in the art will be able to determine what material and thickness to use 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. and 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 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™ ), 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-methoxypro pionates, halogenated hydrocarbons such as chloroform, methylene chloride, and tetrachloroethane, aromatic hydrocarbons such as benzene, toluene, xylene, and cresol, and/or 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 include 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 related 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." (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 term and/or disjunctive phrase representing 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."

As used in the context of describing the present disclosure (particularly in the context of the embodiments below), the terms "a", "an", "the" and similar referents 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 deleted from a group for reasons of convenience and/or patentability. 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 include the best mode known to the inventors for carrying out the present disclosure. Of course, variations on these embodiments will become 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 Embodiment 1 A photoluminescent complex comprising:
A blue light absorbing part,
a linker complex;
a boron-dipyrromethene (BODIPY) moiety;
including;
the linker complex covalently bonds the blue light absorbing moiety and the BODIPY moiety, the blue light absorbing moiety absorbing light energy at a first excitation wavelength and transferring energy to the BODIPY moiety; A photoluminescent complex, wherein the BODIPY moiety absorbs the energy from the blue light absorbing moiety and emits light energy at a second higher wavelength, and the photoluminescent complex has an emission quantum yield of greater than 80%.

Embodiment 2 The photoluminescent complex of Embodiment 1, wherein the blue light absorbing moiety is a xanthenoisoquinoline derivative.

（式中、Ｒ^０は、独立して、水素（Ｈ）、Ｃ_１～Ｃ_３アルキル、任意に置換されたアリール、又は任意に置換されたヘテロアリールから選択される）のものである、実施形態２のフォトルミネッセンス錯体。 Embodiment 3 The xanthenoisoquinoline derivative has the general formula:

(wherein R ⁰ is independently selected from hydrogen (H), C ₁ -C ₃ alkyl, optionally substituted aryl, or optionally substituted heteroaryl) Form 2 photoluminescent complex.

Embodiment 4 The photoluminescent complex of Embodiment 1, wherein the blue light absorbing moiety is a naphthalimide derivative.

（式中、Ｒ^０は、独立して、水素（Ｈ）、置換又は非置換アリール、－ＣＦ_３、３，５－ビス（トリフルオロメチル）フェニル（

）から選択されるか、又はＲ^０に置換基はなく、Ｘは、独立して、酸素（Ｏ）又は硫黄（Ｓ）から選択され、Ｒ^１は、独立して、水素（Ｈ）、置換又は非置換アリール、Ｃ_１～Ｃ_５アルキル、フェニル、３，５－ビス（トリフルオロメチル）フェニル（

）、４－（トリフルオロメチル）フェニル（

）、４－（ｔｅｒｔ－ブチル）フェニル（

）、４－（２－（２－（２－メトキシエトキシ）エトキシ）エトキシ）フェニル（

）から選択されるか、又はＲ^１に置換はない）のものである、実施形態４のフォトルミネッセンス錯体。 Embodiment 5 The naphthalimide derivative has the general formula:

(wherein R ⁰ is independently hydrogen (H), substituted or unsubstituted aryl, -CF ₃ , 3,5-bis(trifluoromethyl)phenyl (

), or there is no substituent on R ⁰ , X is independently selected from oxygen (O) or sulfur (S), and R ¹ is independently selected from hydrogen (H), substituted or unsubstituted aryl, C ₁ -C ₅ alkyl, phenyl, 3,5-bis(trifluoromethyl)phenyl (

), 4-(trifluoromethyl)phenyl (

), 4-(tert-butyl)phenyl (

), 4-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)phenyl(

) or there is no substitution at R ¹ ).

（式中、Ｒ^１及びＲ^６は、独立して、水素（Ｈ）、飽和若しくは不飽和アルキル基、又はアルケン基から選択され、Ｒ^３及びＲ^４は、独立して、Ｃ_１～Ｃ_２アルキルから選択され、Ｒ^２及びＲ^５は、独立して、水素（Ｈ）、飽和アルキル、不飽和アルキル、シアノ（－ＣＮ）、アルキルエステル（－ＣＯＯＣＨ_２ＣＨ_３）、アリールエステル（－ＣＯＯＣＨ_２Ａｒ）、又はＥｔＯ_２Ｃから選択され、Ｒ^７及びＲ^８は、独立して、水素（Ｈ）、メチル基、ハロゲン化物、又はＣ_１～Ｃ_３アルコキシから選択される）のものである、実施形態１のフォトルミネッセンス錯体。 Embodiment 6 The BODIPY portion has the general formula:

(wherein R ¹ and R ⁶ are independently selected from hydrogen (H), a saturated or unsaturated alkyl group, or an alkene group, and R ³ and R ⁴ are independently C ₁ -C ₂ selected from alkyl, R ² and R ⁵ are independently hydrogen (H), saturated alkyl, unsaturated alkyl, cyano (-CN), alkyl ester (-COOCH ₂ CH ₃ ), aryl ester (-COOCH ₂ Ar), or EtO ₂ C, and R ⁷ and R ⁸ are independently selected from hydrogen (H), methyl group, halide, or C ₁ -C ₃ alkoxy; Photoluminescent complex of embodiment 1.

Embodiment 7 R ¹ , R ³ , R ⁴ and R ⁶ are independently selected from C ₁ -C ₃ alkyl or methyl groups, and R ² and R ⁵ are independently C ₁ -C ₃ esters. The photoluminescent complex of embodiment 6 _, wherein R ⁷ _and R ⁸ are independently selected from _methyl groups.

を含む、実施形態１のフォトルミネッセンス錯体。 Embodiment 8 The BODIPY portion has the following structure:

The photoluminescent complex of Embodiment 1, comprising:

を含む、実施形態１のフォトルミネッセンス錯体。 Embodiment 9 The BODIPY portion has the following structure:

The photoluminescent complex of Embodiment 1, comprising:

Embodiment 10 The photoluminescent complex of Embodiment 6, wherein L is a linker complex that can be a substituted ester, an unsubstituted ester, a substituted ether, or an unsubstituted ether.

の１つを含む、実施形態１０のフォトルミネセンス錯体。 Embodiment 11 The unsubstituted ester has the following structure:

The photoluminescent complex of embodiment 10, comprising one of:

の１つを含む、実施形態１０のフォトルミネセンス錯体。 Embodiment 12 The substituted ester has the following structure:

The photoluminescent complex of embodiment 10, comprising one of:

の１つを含む、実施形態１０のフォトルミネッセンス錯体。 Embodiment 13 The unsubstituted and/or substituted ether has the following structure:

The photoluminescent complex of embodiment 10, comprising one of:

のうちの１つを含む、実施形態１、２、３、４、５、６、７、８、９、１０、１１、１２又は１３のフォトルミネッセンス錯体。 Embodiment 14 The photoluminescent complex has the following structure:

The photoluminescent complex of embodiment 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 or 13, comprising one of:

Embodiment 15 A color conversion film, comprising:
a transparent base material layer;
a color conversion layer including a resin matrix;
Embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14, wherein the photoluminescent complex is dispersed within the resin matrix. a photoluminescent complex, comprising a photoluminescent complex;
Including color conversion film.

Embodiment 16 The color conversion film of Embodiment 15 further comprising a singlet oxygen quencher.

Embodiment 17 The color conversion film of Embodiment 15 further comprising a free radical scavenger.

Embodiment 18 The color conversion film of embodiment 15, wherein the color conversion film has a thickness between 10 μm and 200 μm.

Embodiment 19 The color conversion film of Embodiment 15, wherein the color conversion film absorbs light in a wavelength range of about 400 nm to about 480 nm and emits light in a wavelength range of 500 nm to about 560 nm.

Embodiment 20 A method for producing the color conversion film of Embodiment 15, 16, 17, 18 or 19, comprising:
dissolving the photoluminescent complex of embodiment 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14 and the binder resin in a solvent;
applying the mixture to one of the opposing surfaces of a transparent substrate.

Embodiment 21 A backlight unit comprising the color conversion film of Embodiment 15, 16, 17, 18 or 19.

Embodiment 22 A display device including the backlight unit of Embodiment 21.

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 (2.0 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} +): Calcd 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 (PLC) Synthesis of PLC-1

Compound PLC-1.1

Step 1: Ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (1.0 g, 6.0 mmol), 4-hydroxy-2,6-dimethylbenzaldehyde (0.0 g, 6.0 mmol) in 50 mL of 1,2-dichloroethane. A mixture of 449 g, 3.0 mmol) and tosylic acid (50 mg, 0.29 mmol) was degassed and stirred at room temperature overnight. LCMS analysis shows one main peak at m/e+=467.

Step 2: DDQ (0.817 g, 3.6 mmol) was added to the resulting solution and then stirred at room temperature for 30 minutes. LCMS analysis shows that all starting material was converted to the desired product with m/e+=465.

Step 3: 1.7 mL triethylamine and 2.2 mL BF ₃ -diethyl ether were added sequentially to the mixture from step 2 while cooling in an ice bath. The whole was heated at 50° C. for 1 hour. LCMS analysis shows approximately 30% conversion. To this mixture was added another 1 mL of triethylamine and 1 mL of BF ₃ -diethyl ether, and the whole was heated at 50° C. for an additional hour. LCMS analysis shows that all starting material was converted to the desired BODIPY product with m/e+=513, m/e-=512. The reaction mixture was applied directly to silica gel and purified by flash chromatography using an eluent of hexane/ethyl acetate (0%→30% ethyl acetate). The main desired peak was collected and the solvent was removed to give an orange solid (1.0 g, 65% yield). LCMS ( _APCI ): _Calculated for _{C27H32BF2N2O5} (M ₊ H) _: 513.2; Found: 513.1H NMR (400MHz, Chloroform-d) δ 7.26 (s, 3H) , 6.68 (s, 2H), 4.29 (q, J = 7.1Hz, 4H), 2.84 (s, 6H), 2.05 (s, 6H), 1.34 (t, J =7.1Hz, 6H).

Compound PLC-1.2

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 min, then copper powder (0.4 g) was added, followed by 100 mL of Anhydrous DMF was added. 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): Calculated for _C18H10NO6 (M+H): 336.0; Found: 336.1H NMR (400MHz, Chloroform-d) δ 8.80 (dd, J _{= 8} .5, 1.2Hz, 1H), 8.72 (dd, J=7.3, 1.2Hz, 1H), 8.50 (d, J=8.2Hz, 1H), 8.19 (dd, J=8.2, 1.7Hz, 1H), 7.90 (dd, J=8.5, 7.3Hz, 1H), 7.79 (td, J=7.9, 1.7Hz, 1H) , 7.54 (td, J=8.0, 1.3Hz, 1H), 7.39 (dd, J=8.3, 1.2Hz, 1H), 6.89 (d, J=8.2Hz , 1H).

Compound PLC-1.3

A mixture of 4-(2-nitrophenoxyl)-1,8-naphthalic anhydride (2.0 g, 6 mmol) and iron powder (<10 μm, 0.91 g, 16 mmol) in acetic acid (75 mL) was heated for 30 min. It refluxed. 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 give a yellow solid (1.65 g, 90% yield). Confirmed _by LCMS (APCI): Calcd for _C18H12NO4 (M+H): 306.1; _Found : 306.

Compound PLC-1.4

Compound 4-(2-aminophenoxy)-1,8-naphthalic anhydride (1.5 g, 4.9 mmol) was dispersed in acetic acid (35 mL) and 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, and then dried in air and then in vacuo to give a yellow solid (0.92 g, 65% yield). Confirmed by LCMS (APCI): Calculated for C ₁₈ H ₈ O ₄ (M-): 288.0; Found: 288.1H NMR (400 MHz, Chloroform-d) δ 8.61 (dd, J= 17.1, 8.1Hz, 2H), 8.09 (d, J = 8.0Hz, 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-1.5

1H,3H-isochromeno[6,5,4-mna]xanthene-1,3-dione (100 mg, 0.347 mmol), 2-(4-aminophenyl)acetic acid (135 mg, 0.9 mmol) in 5 mL of DMF. The mixture 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): _Calculated for _C26H15NO5 (M-): 421.1; Found: 421.1H NMR (400MHz, DMSO _- d6) δ 8.27 (d, J= 45.1Hz, 4H), 7.67-7.00 (m, 8H), 3.58 (s, 2H).

Compound PLC-1

Compound PLC-1.5 (36 mg, 0.086 mmol), compound PLC-1.1 (40 mg, 0.078 mmol), DMAP/TsOH salt (59 mg, 0.2 mmol) and DIC (0.1 mL) in 5 mL of DCM. , 0.63 mmol) was stirred at room temperature overnight and then at 45° C. for 2 hours. The resulting mixture was applied to silica gel and purified by flash chromatography using an eluent of DCM/ethyl acetate (0%→10% ethyl acetate). The desired product peak was collected and concentrated under reduced pressure. The resulting solid was further washed with methanol and dried in air to give an orange solid (38 mg, 53% yield). Confirmed by LCMS (APCI): Calculated for C ₅₃ H ₄₄ BF ₂ N ₃ O ₉ (M-): 915.3; Found: 915.1H NMR (400 MHz,) δ 8.55 (dd, J = 18.8, 8.1Hz, 2H), 8.04 (d, J = 7.7Hz, 1H), 7.93 (d, J = 8.0Hz, 1H), 7.52 (dd, J = 19.7, 8.0Hz, 3H), 7.40-7.23 (m, 5H), 6.96 (s, 2H), 4.19 (q, J=7.1Hz, 4H), 3. 92 (s, 2H), 3.37 (s, 1H), 2.75 (s, 6H), 2.54 (d, J = 3.3Hz, 1H), 2.06 (s, 6H), 1 .64 (s, 6H), 1.25 (t, J=7.1Hz, 6H).

Synthesis of PLC-2

Compound PLC-2.1

1H,3H-isochromeno[6,5,4-mna]xanthene-1,3-dione (100 mg, 0.347 mmol), 4-(4-aminophenyl)butanoic acid (125 mg, 0.7 mmol) in 5 mL of DMF. ) 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 give a yellow solid (120 mg, 77% yield). Confirmed by LCMS (APCI): Calculated for _C28H19NO5 (M-): 449.1; Found: 449.1H NMR (400MHz, _{DMSO -} d6) δ 8.38 (d, J= 41.6Hz, 4H), 7.81 to 6.97 (m, 8H), 2.69 to 2.64 (m, 2H), 2.26 (t, J=7.2Hz, 2H), 1. 87 (p, J=7.2Hz, 2H).

Compound PLC-2

Compound PLC-1.5 (45 mg, 0.1 mmol), compound PLC-1.1 (40 mg, 0.078 mmol), DMAP/TsOH salt (59 mg, 0.2 mmol) and DIC (0.1 mL) in 5 mL of DCM. , 0.63 mmol) was stirred at room temperature overnight and then at 45° C. for 2 hours. The reaction mixture was loaded onto silica gel and purified by flash chromatography using an eluent of DCM/ethyl acetate (0%→10% ethyl acetate). The desired product peak was collected and concentrated under reduced pressure. The resulting solid was further washed with methanol and dried in air to give an orange solid (46 mg, 62% yield). Confirmed by LCMS ( _APCI ): Calculated for _{C55H49BF2N3O 9} (M ₊ H) _: 944.3; Found: 944.1H NMR (400MHz,) δ 8.54 (dd, J= 18.7, 8.1Hz, 2H), 7.40-7.25 (m, 5H), 7.20 (d, J=8.3Hz, 2H), 6.93 (s, 2H), 4. 19 (q, J = 7.1Hz, 4H), 2.80 (t, J = 7.6Hz, 2H), 2.75 (s, 6H), 2.62 (t, J = 7.4Hz, 2H ), 2.10 (t, J = 7.6 Hz, 2H), 2.06 (s, 6H), 1.65 (s, 6H), 1.25 (t, J = 7.1 Hz, 6H).

Synthesis of PLC-3

Compound PLC-3.1

A mixture of 4-bromo-1,8-naphthalic anhydride (2.77 g, 10 mmol), 4-bromo-2-nitrophenol (3.27 g, 15 mmol) was degassed under vacuum for 30 min and then treated with anhydrous NMP. (50 mL) was added 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 at room temperature overnight to dissolve impurities. Filtration and drying in vacuo gave the desired product as a tan solid (3.3 g, 80% yield). LCMS ( _APCI +): Calculated for _C18H9BrNO6 (M+H) = 413.95; Observed: 414.1H 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-3.2

A mixture of compound PLC-3.1 (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. 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- ): calculated value for _{C18H10BrNO4 =} 382.98; found value: 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-3.3

PLC-3.2 (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, in 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), and then stirred in 50 mL of acetone at 40° C. for 30 minutes. Filtration and drying in air then vacuum gave a tan solid (1.76 g, 70% yield). LCMS ( _APCI +): Calculated 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-3.4

A mixture of PLC-3.3 (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 DMF (8 mL) was heated to room temperature. I degassed it. 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 an 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 pure compound PLC-3.4 as a tan solid (395.0 mg, 73% yield). MS (APCI): calculated for _C26H14BrNO5 ([M ₊ H]+) = ₅₀₀ ; found: 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-3.5

Compound PLC-3.4 (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) was 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 ₄ and concentrated under rotavapor, flash using DCM in EtOAc (0% → 40%, containing 0.1% TFA) as eluent. Purification by chromatography afforded the pure RL-naphthalimide derivative PLC-3.5 as a yellow/tan solid (363.0 mg, 80% yield). MS (APCI): _Calculated value for _C33H18F3NO5 ([M ₊ H]+) = ₅₆₆ ; Observed 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 = 8.0 Hz, 2H), 7.66 (dd, J = 8.0 Hz, J = 4.0 Hz, 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-3

Compound PLC-3.5 (50 mg, 0.089 mmol), compound PLC-3.6 (30 mg, 0.059 mmol), DMAP/TsOH salt (15 mg, 0.051 mmol) and EDC.HCl (60 mg) in 5 mL of DCM. , 0.31 mmol) was stirred at room temperature overnight. The reaction mixture was loaded onto silica gel and purified by flash chromatography using an eluent of DCM/ethyl acetate (0%→10% ethyl acetate). The desired product peak was collected and concentrated under reduced pressure. The resulting solid was reprecipitated with ethyl acetate/methanol and dried in air to give an orange solid (45 mg, in 72%). LCMS ( _{APCI-): Calcd for C60H47BF5N3O9 : 1059.33 ;} Found: 1059.1H NMR ( _400MHz , methylene chloride- _d2 ) δ 8.73 (d, J= 7.9Hz, 1H), 8.66 (d, J = 8.3Hz, 1H), 8.39 (d, J = 2.2Hz, 1H), 8.17 (d, J = 8.0Hz, 1H) ), 7.86 (dt, J = 11.4, 8.4 Hz, 5H), 7.64 (d, J = 8.3 Hz, 2H), 7.57 (d, J = 8.6 Hz, 1H) , 7.43 (d, J=8.3Hz, 1H), 7.41-7.35 (m, 2H), 7.09 (s, 2H), 4.30 (q, J=7.1Hz, 4H), 4.05 (s, 2H), 2.84 (s, 6H), 2.18 (s, 6H), 1.77 (s, 6H), 1.36 (t, J = 7.1Hz , 6H).

Synthesis of PLC-4

Compound PLC-4.1

A 1 L 2N round bottom flask was placed in an aluminum heat block and equipped with a stir bar. 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 amber powder (yield 52%) was obtained. MS (APCI): Calcd for C ₂₂ H ₁₇ NO ₆ (M+H) = 392; Found: 392. 1H NMR (400 MHz, Tetrachloroethane-d ₂ ) δ 8.82 (dd, J = 8.4, 1.2Hz, 1H), 8.71 (dd, J=7.3, 1.2Hz, 1H), 8.49 (d, J=8.3Hz, 1H), 8.16 (d, J=2 .4Hz, 1H), 7.91 (dd, J=8.4, 7.3Hz, 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-4.2

A 250 mL 2N round bottom flask was placed in an aluminum heat block and equipped with a stir bar. The flask was equipped with a finned condenser/gas adapter, a stopper, and a flow control valve. The system was flushed with argon. Compound (6-(4-(tert-butyl)-2-nitrophenoxy)-1H,3H-benzo[de]isochromene-1,3-dione) (10.0 mmol, 3.914 g) and 2-MeTHF were placed in a flask. (70 mL) was added. 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 ): Calcd for _C22H19NO4 (M+H) = ₃₆₂ ; Found: 362. ¹ H NMR (400 MHz, tetrachloroethane-d ₂ ) δ 8.88 (dd, J=8.4, 1.2 Hz, 1H), 8.69 (dd, J=7.3, 1.2 Hz, 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-4.3

A 40 mL vial was charged with a stir bar, NaNO ₂ (30.0 mmol, 2.070 g), and water (10 mL). The vial was stirred in an ice water bath at 0°C. A stir bar and a compound (6-(2-amino-4-(tert-butyl)phenoxy)-1H,3H-benzo[de]isochromene-1,3-dione) (4.00 mmol, 1 .446g) was added. 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 a dropping funnel and the diazo solution was added dropwise with high speed 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. Purified by flash chromatography on silica gel (220 g, solid, equilibrated 50% DCM/Hexane, elution 50% DCM/Hexane (2 CV) → 100% DCM (20 CV) → Isocratic DCM (15 CV) → 0% EtOAc/DCM (0CV) → 1% EtOAc/DCM (10CV)). product tail. Fractions containing product were evaporated to dryness in vacuo. Obtained 528 mg (38% yield). MS ( _APCI ): Calcd for _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-4.4

Compound PLC-4.4 was dissolved in 9-(tert-butyl)-1H,3H-isochromeno[6,5,4-mna]xanthene-1,3- of compound PLC-4.3 in anhydrous DMF (10 mL). It was synthesized from dione (1.191 mmol, 410 mg) and 2-(4-aminophenyl)acetic acid (2.98 mmol, 450 mg), and the mixture was heated at 160° C. for 2 hours. After work-up and precipitation, 579 mg of product (quantitative yield) was obtained. MS ( _APCI ): Calcd for _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-4

PLC-4 was added to PLC-1.1 (0.050 mmol, 39.9 mg) and 2-(4-(tert-butyl)-1,3- of PLC-4.4 in the same manner as PLC-3). Dioxo-1H-xanteno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid (0.075 mmol, 35.8 mg), DMAP pTsOH salt (0.100 mmol, 29.4 mg), and EDC·HCl (0.075 mmol, 14.4 mg). The crude product was purified in the usual manner and triturated with hot MeOH. The product was dried in a vacuum oven at about 110°C. Obtained 44.1 mg of an orange solid (91% yield). MS ₍ APCI): Calcd for _C30H23NO5 ( _M- ) = 971; Found: 971. ¹ H NMR (400 MHz, methylene chloride-d ₂ ) δ 8.66 (d, J = 7.9 Hz, 1H), 8.59 (d, J = 8.3 Hz, 1H), 8.13 (d, J = 2.3Hz, 1H), 8.06 (d, J = 8.0Hz, 1H), 7.64 (dd, J = 8.7, 2.3Hz, 1H), 7.62 to 7.56 ( m, 2H), 7.39-7.30 (m, 4H), 7.05 (s, 2H), 4.27 (q, J = 7.1Hz, 4H), 4.01 (s, 2H) , 2.80 (s, 6H), 2.14 (s, 6H), 1.73 (s, 6H), 1.44 (s, 9H), 1.32 (t, J = 7.1Hz, 6H ).

Synthesis of compound PLC-5

Compound PLC-5.1

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-5.2

PLC-5.1 (1576-85) (190 mg, 0.426 mmol), 4-(4-aminophenyl)butanoic acid (180 mg, 0.64 mmol) in anhydrous N,N-dimethylformamide (DMF) (4 mL). , 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 under vacuum at 90 °C for 1 hour to give a yellow solid (220 mg, 84.5% yield). . 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-5.3

Compound PLC-5.2 (100 mg, 0.165 mmol), (3,5-bis(trifluoromethyl)phenyl)boronic acid (170 mg, 0.66 mmol), Pd in THF/water (5 mL/0.5 mL) A mixture of (dppf)Cl ₂ (20 mg, 0.027 mmol) and potassium carbonate (138 mg, 1 mmol) 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-5

PLC-3.6 (1576-30) (30 mg, 0.058 mmol), PLC-5.3 (1576-88) (70 mg, 0.008 mmol), DIC (0.1 mL, 0.63 mmol) in DCM (5 mL) and DMAP/p-TsOH (30 mg, 0.1 mmol) was stirred at room temperature for 40 hours. The resulting mixture was then loaded onto silica gel and purified by flash chromatography using an eluent of DCM/ethyl acetate (0%→5% ethyl acetate). The desired main orange fraction was collected. After removing the solvent, the resulting solid was washed with methanol. After filtration, the desired product was obtained as an orange solid (61 mg, 77% yield) and dried in air. LCMS _{(APCI-): Calcd for C71H52BF14N3O9 = 1367.36 ; Found} : 1367. ^1H NMR (400MHz, _d2 -TCE) δ 8.66 (s, 1H), 8.41 (s, 1H), 8.18 (s, 2H), 7.96 (d, J = 18.8Hz , 4H), 7.38 (d, J = 8.2Hz, 3H), 7.20 (dd, J = 14.5, 8.3Hz, 3H), 7.02 to 6.84 (m, 4H) , 4.19 (q, J=7.2Hz, 4H), 2.80 (m, 2H), 2.75 (s, 6H), 2.61 (t, J=7.3Hz, 2H), 2 .10 (m, 2H), 2.06 (s, 6H), 1.64 (s, 6H), 1.25 (t, J=7.1Hz, 6H).

Synthesis of compound PLC-6

Compound PLC-6.1

A mixture of PLC-3.3 (550 mg, 1.5 mmol), 4-(4-aminophenyl)butanoic acid (537 mg, 3 mmol) and DMAP (12.2 mg, 0.1 mmol) in 10 mL of DMF was subjected to microwave reaction. It was heated in a vessel 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-6.2

PLC-6.1 (385 mg, 0.729 mmol), 3,5-bis-(trifluoromethyl)phenylboronic acid (374 mg, 1.45 mmol) in cosolvent of THF/DMF/water (20 mL/4 mL/2 mL) ), Pd(dppf)Cl ₂ (36 mg, 0.05 mmol), potassium carbonate (276 mg, 2 mmol) was degassed and then heated at 80° C. overnight. The mixture was worked up with 200 mL of ethyl acetate and 50 mL of 0.6N aqueous hydrochloric acid. The aqueous layer 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 diluted with DCM/EA (0% → 40% EA containing 0.1% TFA). ) was purified by flash chromatography using an eluent of 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

PLC-6.2 (49 mg, 0.075 mmol), PLC-3.6 (25.6 mg, 0.05 mmol), DMAP/TsOH salt (20 mg, 0.068 mmol) and DIC (0.1 mL) in 5 mL of DCM. , 0.63 mmol) was stirred at room temperature overnight. The reaction mixture was loaded onto silica gel and purified by flash chromatography using an eluent of DCM/ethyl acetate (0%→10% ethyl acetate). The desired product peak was collected and concentrated under reduced pressure. The resulting solid was further washed with methanol and dried in air to yield an orange solid (50 mg, 86% in). LCMS _{(APCI-): Calcd for C63H50BF8N3O9 ( M- )} : 1155.35; _Found : 1155. ^1H NMR (400MHz, d2-TCE) δ 8.60 (d, J = 7.9Hz, 1H), 8.55 (d, J = 8.4Hz, 1H), 8.18 (d, J = 2 .2Hz, 1H), 8.05 (d, J = 8.1Hz, 1H), 8.03 to 7.99 (m, 2H), 7.87 (s, 1H), 7.72 (dd, J = 8.6, 2.2Hz, 1H), 7.48 (d, J = 8.6Hz, 1H), 7.36 (dd, J = 15.9, 8.2Hz, 3H), 7.21 ( d, J = 8.2Hz, 2H), 6.93 (s, 2H), 4.19 (q, J = 7.1Hz, 4H), 2.81 (t, J = 7.5Hz, 2H), 2.75 (s, 6H), 2.62 (t, J=7.4Hz, 2H), 2.11 (t, J=7.5Hz, 2H), 2.06 (s, 6H), 1. 65 (s, 6H), 1.25 (t, J=7.1Hz, 6H).

Synthesis of compound PLC-7

Compound PLC-7.1

1H,3H-thioxanteno[2,1,9-def]isochromene-1,3-dione (458 mg, 1.5 mmol), 4-(4-aminophenyl)butanoic acid (537 mg, 3 mmol) and A mixture of DMAP (14 mg, 0.11 mmol) was heated in a microwave reactor at 165° C. for 2.5 hours. The resulting solution was added dropwise to 60 mL of acetone while stirring. An orange precipitate was formed, which was filtered, washed with diethyl ether and dried in air to obtain an orange solid (546 mg), which was further dried in a vacuum oven at 100 °C for 3 hours to obtain the desired The product was obtained as an orange solid (500 mg, 71.7% yield). Confirmed by LCMS (APCI-): Calcd for C ₂₈ H ₁₉ NO ₄ S (M-) = 465.10; Found: 465. ^1H NMR (400MHz, DMSO- _d6 ) δ 8.55 (d, J=8.4Hz, 1H), 8.52-8.46 (m, 2H), 8.32 (d, J=8. 0Hz, 1H), 7.78 (d, J = 8.0Hz, 1H), 7.65 to 7.58 (m, 1H), 7.52 (tt, J = 7.2, 5.5Hz, 2H ), 7.37 to 7.30 (m, 2H), 7.30 to 7.23 (m, 2H), 2.69 (t, J = 7.4Hz, 2H), 2.29 (t, J = 7.3Hz, 2H), 1.88 (p, J = 7.5Hz, 2H).

Compound PLC-7

PLC-3.6 (25.6 mg, 0.05 mmol), PLC-7.1 (35 mg, 0.075 mmol), EDC·HCl (110 mg, 0.57 mmol) and DMAP/p-TsOH in DCM (5 mL). (20 mg, 0.068 mmol) was stirred at room temperature overnight. The resulting mixture was then loaded onto silica gel and purified by flash chromatography using an eluent of DCM/ethyl acetate (0%→5% ethyl acetate). The main green fraction was collected, concentrated under reduced pressure, and then triturated with methanol. After filtration and drying in air, an orange solid (40 mg, 83% yield) was obtained. LCMS _{( APCI-} ): Calcd _{for C55H48BF2N3O8S} (M-) = _959.32 ; Found: 959. ^1H NMR (400MHz, d2-TCE) δ 8.56 (d, J=8.1Hz, 1H), 8.35 (d, J=8.0Hz, 1H), 8.19 (dd, J=8 .7, 4.4Hz, 2H), 7.51 (d, J = 8.0Hz, 1H), 7.45 to 7.30 (m, 5H), 7.20 (d, J = 8.2Hz, 2H), 6.93 (s, 2H), 4.19 (q, J = 7.1Hz, 4H), 2.80 (t, J = 7.6Hz, 2H), 2.75 (s, 6H) , 2.62 (t, J=7.5Hz, 2H), 2.11 (q, J=7.6Hz, 2H), 2.06 (s, 6H), 1.65 (s, 6H), 1 .25 (t, J=7.1Hz, 6H).

Synthesis of compound PLC-8

Compound PLC-8.1

Compound PLC-6.1 (385 mg, 0.729 mmol), phenylboronic acid (178 mg, 1.45 mmol), Pd(dppf)Cl ₂ (36 mg) in cosolvent of THF/DMF/water (20 mL/4 mL/2 mL). , 0.05 mmol), potassium carbonate (276 mg, 2 mmol) was degassed and then heated at 80° 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 removed under reduced pressure to give a yellow solid (250 mg, 65% yield). LCMS ( _APCI- ): Calcd for _C34H23NO5 : 525.16; Found: ₅₂₅ . ^1H NMR (400MHz, TCE-d2) δ 8.55 (dd, J=19.5, 8.1Hz, 2H), 8.20 (d, J=2.1Hz, 1H), 8.01 (d , J=8.1Hz, 1H), 7.72 (dd, J=8.6, 2.1Hz, 1H), 7.62 (d, J=7.3Hz, 2H), 7.51 to 7. 28 (m, 7H), 7.17 (d, J = 8.2Hz, 2H), 2.72 (t, J = 7.7Hz, 2H), 2.39 (t, J = 7.3Hz, 2H ), 1.99 (q, J = 7.2Hz, 2H).

Compound PLC-8

Compounds PLC-8.1 (39.4 mg, 0.075 mmol), PLC-3.6 (25.6 mg, 0.05 mmol), DIC (0.1 mL, 0.63 mmol), DMAP/in DCM (5 mL). A mixture of TsOH (20 mg, 0.068 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/EA (0%→10% EA). The desired main fractions were collected, concentrated under reduced pressure, and reprecipitated in DCM/methanol to give an orange solid (45 mg, 88% yield). LCMA (APCI-): Calcd for C ₆₁ H ₅₂ BF ₂ N ₃ O ₉ : 1019.38; Found: 1019. ^1H NMR (400MHz, d2-TCE) δ 8.56 (dd, J=19.5, 8.1Hz, 2H), 8.20 (d, J=2.1Hz, 1H), 8.02 (d , J=8.1Hz, 1H), 7.73 (dd, J=8.6, 2.1Hz, 1H), 7.66 to 7.58 (m, 2H), 7.45 (q, J= 8.4, 7.9Hz, 3H), 7.37 (dd, J = 7.8, 5.7Hz, 3H), 7.32 (d, J = 8.4Hz, 1H), 7.21 (d , J=8.2Hz, 2H), 6.93 (s, 2H), 4.19 (q, J=7.1Hz, 4H), 2.81 (t, J=7.6Hz, 2H), 2 .75 (s, 6H), 2.62 (t, J = 7.5Hz, 2H), 2.11 (q, J = 7.6Hz, 2H), 2.06 (s, 6H), 1.65 (s, 6H), 1.25 (t, J=7.1Hz, 6H).

Synthesis of compound PLC-9

Compound PLC-9.1

A mixture of 4-bromo-1,8-naphthalic anhydride (2.77 g, 10 mmol), 4-bromo-2-nitrophenol (3.27 g, 15 mmol) was degassed under vacuum for 30 min and then treated with anhydrous NMP. (50 mL) was added 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 at room temperature overnight 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. ^1H 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-9.2

A mixture of PLC-9.1 (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. 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-9.3

PLC-9.2 (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 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-9.4

A mixture of PLC-9.3 (550 mg, 1.5 mmol), 4-(4-aminophenyl)butanoic acid (537 mg, 3 mmol) and DMAP (12.2 mg, 0.1 mmol) in 10 mL of DMF was subjected to microwave reaction. It was heated in a vessel 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-9.4
Compound PLC-9.5

PLC-9.4 (385 mg, 0.729 mmol), 3,5-bis-(trifluoromethyl)phenylboronic acid (374 mg, 1.45 mmol) in cosolvent of THF/DMF/water (20 mL/4 mL/2 mL). ), Pd(dppf)Cl ₂ (36 mg, 0.05 mmol), potassium carbonate (276 mg, 2 mmol) was degassed and then heated at 80° 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 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), 2.04-1.97 (m, 2H).

Compound PLC-1.1

Step 1: Ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (1.0 g, 6.0 mmol), 4-hydroxy-2,6-dimethylbenzaldehyde (0.0 g, 6.0 mmol) in 50 mL of 1,2-dichloroethane. A mixture of 449 g, 3.0 mmol) and tosylic acid (50 mg, 0.29 mmol) was degassed and stirred at room temperature overnight. LCMS analysis shows one main peak at m/e ⁺ =467.

Step 2: DDQ (0.817 g, 3.6 mmol) was added to the resulting solution and then stirred at room temperature for 30 minutes. LCMS analysis shows that all starting material was converted to the desired product with m/e ⁺ =465.

Step 3: With ice bath cooling, 1.7 mL triethylamine and 2.2 mL BF ₃ -diethyl ether were added sequentially to the mixture from step 2. The whole was heated at 50°C for 1 hour. LCMS analysis shows approximately 30% conversion. To this mixture was added an additional 1 mL of triethylamine and 1 mL of BF ₃ -diethyl ether, and the whole was heated at 50° C. for an additional hour. LCMS analysis shows that all starting material was converted to the desired BODIPY product with m/e ⁺ =513, m/e ⁻ =512. The reaction mixture was applied directly to silica gel and purified by flash chromatography using an eluent of hexane/ethyl acetate (0%→30% ethyl acetate). The main desired peak was collected and the solvent was removed to give an orange solid (1.0 g, 65% yield). LCMS _{( APCI): Calcd for C27H32BF2N2O5 ( M +} H): 513.2; Found: 513. ^1H NMR (400MHz, chloroform-d) δ 7.26 (s, 3H), 6.68 (s, 2H), 4.29 (q, J = 7.1Hz, 4H), 2.84 (s, 6H), 2.05 (s, 6H), 1.34 (t, J=7.1Hz, 6H).

Compound PLC-9

PLC-9.5 (49 mg, 0.075 mmol), PLC-3.6 (25.6 mg, 0.05 mmol), DMAP/TsOH salt (20 mg, 0.068 mmol) and DIC (0.1 mL) in 5 mL of DCM. , 0.63 mmol) was stirred at room temperature overnight. The reaction mixture was loaded onto silica gel and purified by flash chromatography using an eluent of DCM/ethyl acetate (0%→10% ethyl acetate). The desired product peak was collected and concentrated under reduced pressure. The resulting solid was further washed with methanol and dried in air to yield an orange solid (50 mg, 86% in). LCMS _{(APCI-): Calcd for C63H50BF8N3O9 ( M- )} : 1155.35; _Found : 1155. ^1H NMR (400MHz, d2-TCE) δ 8.60 (d, J = 7.9Hz, 1H), 8.55 (d, J = 8.4Hz, 1H), 8.18 (d, J = 2 .2Hz, 1H), 8.05 (d, J = 8.1Hz, 1H), 8.03 to 7.99 (m, 2H), 7.87 (s, 1H), 7.72 (dd, J = 8.6, 2.2Hz, 1H), 7.48 (d, J = 8.6Hz, 1H), 7.36 (dd, J = 15.9, 8.2Hz, 3H), 7.21 ( d, J = 8.2Hz, 2H), 6.93 (s, 2H), 4.19 (q, J = 7.1Hz, 4H), 2.81 (t, J = 7.5Hz, 2H), 2.75 (s, 6H), 2.62 (t, J=7.4Hz, 2H), 2.11 (t, J=7.5Hz, 2H), 2.06 (s, 6H), 1. 65 (s, 6H), 1.25 (t, J=7.1Hz, 6H).

Synthesis of compound PLC-10

Compound PLC-10.1

A 1 L 2N round bottom flask was placed in an aluminum heat block and equipped with a stir bar. 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 containing 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 amber powder (yield 52%) was obtained. MS ( _APCI ): Calcd for _C22H17NO6 (M+H) ₌ 392; Found: 392. ¹ H NMR (400 MHz, tetrachloroethane-d ₂ ) δ 8.82 (dd, J=8.4, 1.2 Hz, 1H), 8.71 (dd, J=7.3, 1.2 Hz, 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-10.2

A 250 mL 2N round bottom flask was placed in an aluminum heat block and equipped with a stir bar. The flask was equipped with a finned condenser/gas adapter, a stopper, and a flow control valve. The system was flushed with argon. PLC-10.1 (10.0 mmol, 3.914 g) and 2-MeTHF (70 mL) were added to the flask. While stirring at room temperature, HCl (100 mmol, 4.0 N, 25 mL) in water and _SnCl2.2H2O ( _40.0 mmol, 9.024 g) were added. 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 ): Calcd for _C22H19NO4 (M+H) = ₃₆₂ ; Found: 362. ¹ H NMR (400 MHz, tetrachloroethane-d ₂ ) δ 8.88 (dd, J=8.4, 1.2 Hz, 1H), 8.69 (dd, J=7.3, 1.2 Hz, 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-10.3

A 40 mL vial was charged with a stir bar, NaNO ₂ (30.0 mmol, 2.070 g), and water (10 mL). The vial was stirred in an ice water bath at 0°C. A stir bar and PLC-10.2 (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. Purified by silica gel flash chromatography (220 g, solid, equilibrated 50% DCM/Hexane, elution 50% DCM/Hexane (2 CV) → 100% DCM (20 CV) → Isocratic DCM (15 CV) → 0% EtOAc/ DCM (0CV) → 1% EtOAc/DCM (10CV)). product tail. Fractions containing product were evaporated to dryness in vacuo. Obtained 528 mg (38% yield). MS ( _APCI ): Calcd for _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-10.4

PLC-10.4 was mixed with PLC-10.3 (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): Calcd for _C32H27NO5 (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-10

Compound 10 was added to PLC-1.1 (0.050 mmol, 25.6 mg), PLC-10.4 (0.075 mmol, 37.9 mg), DMAP pTsOH salt (0.100 mmol, 29.4 mg) and EDC·HCl (0.075 mmol, 14.4 mg). The crude reaction mixture was diluted with hexane (20 mL) and loaded onto approximately 15 g of flash silica gel in a loader. Purified by flash chromatography (120 g, solid, equilibrated 80% DCM/Hexane, elution 80% DCM/Hexane (2 CV) → 100% DCM (10 CV) → Isocratic DCM (10 CV) → 0% EtOAc/DCM (0CV) → 2% EtOAc/DCM (30CV)). Fractions containing product were evaporated to dryness. The product was triturated with hot MeOH. The solid was dried in a vacuum oven at about 110°C. 46.5 mg (yield 93%) of an orange solid was obtained. MS _{(APCI): Calcd for C57H52BF2N3O9 ( M- ) =} 999; Found: 999. ¹ H NMR (400 MHz, tetrachloroethane-d ₂ ) δ 8.66 (d, J = 7.9 Hz, 1H), 8.60 (d, J = 8.4 Hz, 1H), 8.08 (d, J = 2.3Hz, 1H), 8.05 (d, J = 8.1Hz, 1H), 7.64 (dd, J = 8.8, 2.2Hz, 1H), 7.49 to 7.43 ( m, 2H), 7.41 to 7.34 (m, 2H), 7.32 to 7.27 (m, 2H), 7.02 (s, 2H), 4.28 (q, J = 7. 1Hz, 4H), 2.89 (t, J=7.6Hz, 2H), 2.84 (s, 6H), 2.71 (t, J=7.4Hz, 2H), 2.26 to 2. 11 (m, 8H), 1.45 (s, 9H), 1.34 (t, J=7.1Hz, 6H).

Synthesis of compound PLC-11

Compound PLC-11.1

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 value for _C20H10BrNO5 ( _MH ) ₌ 423; Observed value: 423. 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 = 8.0 Hz, 2H), 7.58 (d, J = 8.6 Hz, 1H), 7.45 (d, J = 8.4 Hz, 1H), 4.71 ( s, 2H).

Compound PLC-11.2

PLC-11.1 (7.0 g, 16.50 mmol, 1 eq.) was suspended in 2-MeTHF (150 ml) and 4-(trifluoromethyl)benzeneboronic acid (5.648 g, 29.7 mmol, 1.8 ), _K2CO3 (4.65 _g , 33 mmol, 2 eq.), _H2O (15 ml), Pd(dppf) _Cl2.DCM (269.5 mg, 0.33 mmol, 0.02 eq.) were 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): Calcd for _C27H14F3NO5 ( _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-11

PLC-11.2 (73.4 mg, 0.15 mmol, 1.5 eq.) was suspended in anhydrous DCM (10.0 ml), PLC-11.3 (51.2 mg, 0.100 mmol, 1 eq.), DMAP -pTSA (58.8 mg, 0.2 mmol, 2 equivalents) and EDC·HCl (57.5 mg, 0.3 mmol, 3 equivalents) were added, and the mixture was stirred at room temperature under an argon atmosphere for 5 hours. Diluted with DCM (150 ml), filtered, washed the solid with 50 ml of DCM, collected the filtrate and loaded onto an 80 g SiO column, Hex-DCM ( _1/1 ), DCM only, then DCM in DCM. After elution with 0.5% EA and washing with MeOH, 87 mg of yellow solid was obtained (78% yield). MS ₍ APCI) _: Calcd _{for C54H43BF5N3O9 (} M-) ₌ 983; Found: 983. ¹ H NMR (400 MHz) δ 8.64 (d, J = 7.9 Hz, 1 H), 8.59 (d, J = 8.3 Hz, 1 H), 8.20 (d, J = 2.1 Hz, 1 H ), 8.03 (d, J=8.2Hz, 1H), 7.72 (dd, J=8.5, 2.0Hz, 4H), 7.46 (d, J=8.6Hz, 1H) , 7.34 (d, J = 8.4 Hz, 1H), 7.01 (s, 2H), 5.15 (s, 2H), 4.17 (q, J = 7.1Hz, 4H), 2 .74 (s, 6H), 2.06 (s, 5H), 1.96 (s, 1H), 1.61 (s, 5H), 1.51 (s, 12H), 1.23 (t, J=7.1Hz, 5H).

Synthesis of compound PLC-12

PLC-11.2 (73.4 mg, 0.15 mmol, 3 eq.) was suspended in anhydrous DCM (10.0 ml), PLC-12.1 (39.93 mg, 0.05 mmol, 1 eq.), DMAP-pTSA (58.8 mg, 0.2 mmol, 4 eq.), added EDC.HCl (47.92 mg, 0.25 mmol, 5 eq.), stirred at room temperature under argon atmosphere for 5 h, diluted with DCM (150 ml), Filter, wash the solid with 50 ml of DCM, collect the filtrate and load onto an 80 g SiO column and elute with Hex-DCM (1/1), DCM only, then 0.5% EA in DCM. , followed by washing with MeOH, 80 mg, yield 77% was obtained. MS ₍ APCI) _: Calcd for _{C64H47BF5N3O9} (M- _{) =} 1107; Found: 1107. ^1H NMR (400MHz,) δ 8.64 (d, J = 7.9Hz, 1H), 8.59 (d, J = 8.4Hz, 1H), 8.20 (d, J = 2.1Hz, 1H), 8.03 (d, J = 8.1Hz, 1H), 7.72 (dd, J = 8.5, 2.1Hz, 4H), 7.46 (d, J = 8.6Hz, 1H ), 7.34 (d, J=8.3Hz, 1H), 7.32-7.18 (m, 9H), 7.00 (s, 2H), 5.17 (s, 4H), 5. 14 (s, 2H), 2.74 (s, 6H), 2.04 (s, 6H), 1.61 (s, 6H).

Synthesis of compound PLC-13

Compound PLC-13.1

PLC-6.1 (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): Calcd for _C20H10BrNO5 ( _MH ) = 423; Found: 423. ^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-13.2

PLC-13.1 (4.24 g, 10.0 mmol, 1 eq.) was suspended in 2-MeTHF (150 ml), H ₂ O (5.0 ml), and 4-(tert-butyl)benzeneboronic 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) were 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): Calcd for _C30H23NO5 ( _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-13

PLC-13.2 (71.62 mg, 0.15 mmol, 1.5 eq.) was suspended in anhydrous DCM (10.0 ml), PLC-13.3 (58.5 mg, 0.1 mmol, 1 eq.), DMAP - Add pTSA (58.8 mg, 0.2 mmol, 2 eq.), EDC.HCl (57.5 mg, 0.3 mmol, 3 eq.), stir at room temperature under argon atmosphere for 5 hours, and dilute with DCM (150 ml). filtered, washed the solid with 50 ml of DCM, collected the filtrate and loaded onto an 80 g _SiO2 column with Hex-DCM (1/1), DCM only, then 0.5% EA in DCM. It eluted. The crude material was loaded onto a 80 g SiO _column and eluted with Hex-DCM (1/1), DCM only, then 0.5% EA in DCM, then washed with MeOH, 80 mg, yield 84.3 I got %. MS _{(APCI): Calcd for C57H52BF2N3O9 ( M- ) =} 971; Found: 971. ^1H NMR (400MHz,) δ 8.64 (d, J = 7.9Hz, 1H), 8.59 (d, J = 8.4Hz, 1H), 8.20 (d, J = 2.1Hz, 1H), 8.03 (d, J = 8.1Hz, 1H), 7.72 (dd, J = 8.5, 2.1Hz, 4H), 7.46 (d, J = 8.6Hz, 1H ), 7.34 (d, J=8.3Hz, 1H), 7.32-7.18 (m, 9H), 7.00 (s, 2H), 5.17 (s, 4H), 5. 14 (s, 2H), 2.74 (s, 6H), 2.04 (s, 6H), 1.61 (s, 6H).

Synthesis of compound PLC-14

PLC-13.2 (71.62 mg, 0.15 mmol, 1.5 eq.) was suspended in anhydrous DCM (10.0 ml), PLC-12.1 (63.65 mg, 0.100 mmol, 1 eq.), DMAP - Add pTSA (58.8 mg, 0.2 mmol, 2 eq.), EDC.HCl (57.5 mg, 0.3 mmol, 3 eq.), stir at room temperature under argon atmosphere for 5 hours, and dilute with DCM (150 ml). filtered, washed the solid with 50 ml of DCM, collected the filtrate and loaded onto an 80 g _SiO2 column with Hex-DCM (1/1), DCM only, then 0.5% EA in DCM. It eluted. The good fractions were concentrated and then washed with MeOH to give 85 mg, 77% yield. MS ₍ APCI) _: Calcd for _{C67H56BF2N3O9} ( _M- ) = 1095; _Found : 1095. ^1H NMR (400MHz) δ 8.63 (d, J = 7.9Hz 1H), 8.58 (d, J = 8.4Hz, 1H), 8.21 (d, J = 2.1Hz, 1H), 8.02 (d, J=8.1Hz, 1H), 7.73 (dd, J=8.6, 2.1Hz, 1H), 7.56 (d, J=8.3Hz, 2H), 7 .46 (d, J=8.4Hz, 2H), 7.42 (d, J=8.6Hz, 1H), 7.32 (d, J=8.4Hz, 1H), 7.30-7. 17 (m, 10H), 7.00 (s, 2H), 5.17 (s, 5H), 5.14 (s, 2H), 2.74 (s, 6H), 2.04 (s, 6H) ), 1.61 (s, 6H), 1.31 (s, 9H).

Synthesis of compound PLC-15

Compound PLC-3.4

A mixture of PLC-3.3 (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 DMF (8 mL) was heated to room temperature. I degassed it. 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 pure compound PLC-3.4 as a tan solid (395.0 mg, 73% yield). MS ₍ APCI): _Calcd for _C26H14BrNO5 ([M+H] ⁺ ) = 500; Found: 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-15.1

PLC-3.4 (175.0 mg, 0.35 mmol), 4-tert-butylphenylboronic acid (124.6 mg, 0.70 mmol), Pd in THF-DMF-H ₂ O (10 mL/2 mL/1 mL). (dppf) A mixture of _Cl2 (18.0 _mg , 0.025 mmol) and _K2CO3 (130.4 mg, 0.95 mmol) was degassed at room temperature. The mixture was then heated to 80°C and kept at this temperature overnight. TLC and LCMS showed the reaction was complete. The mixture was cooled to room temperature. Then 0.1 HCl (75 mL) and EtOAc (75 mL) were added to it. After separation in a separatory funnel, the aqueous solution was saturated with NaCl and further extracted with THF (75 mL x 3). The combined organic phases were dried over _{anhydrous Na2SO4} , then filtered, concentrated under a rotary evaporator, and flash chromatographed on silica gel using 0% → 40% EtOAc in DCM with 0.1% TFA as eluent. Purification by graphics gave PLC-15.1 (76.0 mg, 39% yield) as a yellow solid. MS (APCI): Calcd for C ₃₆ H ₂₇ NO ₅ ([MH] ^- ) = 553; Found: 553. ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) δ 8.69 (d, J = 8.0 Hz, 1H), 8.64 (d, J = 8.4 Hz, 1H), 8.24 (d, J = 8.4Hz, 1H), 8.03 (d, J = 8.0Hz, 1H), 7.76 (dd, J = 8.4Hz, 2.0Hz, 1H), 7.53 (m, 7H), 7.33 (m, 4H), 3.77 (s, 2H), 1.40 (s, 9H).

Compound PLC-15

In a vial, PLC-1.1 (30.0 mg, 0.059 mmol), PLC-15.1 (64.8 mg, 0.12 mmol), EDC・HCl (56.6 mg, 0.30 mmol), and DMAP・TsOH (35.4 mg, 0.12 mmol) was added followed by anhydrous DCM (3 ml). The reaction mixture was kept at room temperature overnight. After completion of the reaction, the mixture was loaded on silica gel and purified by flash chromatography using DCM in EtOAc (0%→4%) as eluent to give pure RL-naphthalimide-BODIPY PLC- as an orange-yellow solid. I got 15. The solid was further triturated with EtOAc (0.5 mL) and MeOH (15 ml) to give RL-naphthalimide-BODIPY PLC-15 (48.0 mg, 78% yield). MS (APCI): Calcd for C ₆₃ H ₅₆ BF ₂ N ₃ O ₉ ([MH] ^- ) = 1047; Found: 1047. ^1H NMR (400MHz, _CDCl2CDCl2 ) 8.68 (d, J=8.0Hz, _1H ), 8.63 (d, J=8.0Hz, 1H), 8.30 (d, J=2 .0Hz, 1H), 8.10 (d, J = 8.0Hz, 1H), 7.82 (dd, J = 8.0Hz, 2.0Hz, 1H), 7.65 (m, 4H), 7 .53 (m, 3H), 7.39 (m, 3H), 7.05 (s, 2H), 4.28 (q, J = 7.2Hz, 4H), 4.01 (s, 2H), 2.84 (s, 6H), 2.16 (s, 6H), 1.74 (s, 6H), 1.40 (s, 9H), 1.34 (t, J=7.2Hz, 6H) .

Synthesis of compound PLC-16

Compound PLC-16.1

A stirring bar was attached to the 100 mL vial. PLC-3.4 (400.0 mg, 0.80 mmol), 3,5-bis(trifluoromethyl)phenylboronic acid in THF/DMF/H ₂ O (22 ml/4.4 ml/2.2 ml) in a vial. (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 Na2SO4} , 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-16.1 was obtained as a yellow/tan solid (311.0 mg, 61% yield). MS ₍ APCI): Calcd _{for C34H17F6NO5} ([M+H] ⁺ ) = 634; Found: 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-16

A 25 mL vial was equipped with a stir bar. In a vial, PLC-1.1 (40.0 mg, 0.078 mmol), PLC-16.1 (98.9 mg, 0.16 mmol), EDC・HCl (74.8 mg, 0.39 mmol) and DMAP・TsOH ( 46.8 mg, 0.16 mmol) was added followed by dry DCM (4 ml). The reaction mixture was kept at room temperature overnight. After completion of the reaction, the mixture was loaded on silica gel and purified by flash chromatography using DCM in EtOAc (0%→4%) as eluent to give pure RL-naphthalimide-BODIPY PLC- as an orange-yellow solid. I got 16. The solid was further triturated with EtOAc (0.5 mL) and MeOH (15 ml) to give RL-naphthalimide-BODIPY PLC-16 (58.0 mg, 66% yield). MS (APCI): Calcd for C ₆₁ H ₄₆ BF ₈ N ₃ O ₉ ([MH] ^- ) = 1127; Found: 1127. ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) 8.70 (d, J = 8.0 Hz, 1 H), 8.65 (d, J = 8.0 Hz, 1 H), 8.28 (d, J = 2 .4Hz, 1H), 8.15 (d, J = 8.0Hz, 1H), 8.11 (m, 2H), 7.96 (bs, 1H), 7.81 (dd, J = 8.0Hz , 2.4Hz, 1H), 7.61 (m, 3H), 7.41 (m, 3H), 7.05 (s, 2H), 4.28 (q, J = 7.2Hz, 4H), 4.01 (s, 2H), 2.84 (s, 6H), 2.16 (s, 6H), 1.73 (s, 6H), 1.34 (t, J = 7.2Hz, 6H) .

Synthesis of compound PLC-17

Compound PLC-17.1

A 250 mL 2N round bottom flask was placed in an aluminum heat block and equipped with a stir bar. The flask was fitted with a finned condenser/gas adapter and a flow control valve. The system was flushed with argon. 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol (11.0 mmol, 2.421 g), 1-bromo-2-(2-(2 -methoxyethoxy)ethoxy)ethane (10.0 mmol, 2.48 mL), anhydrous DMF (25 mL), and K ₂ CO ₃ (11.0 mmol, 1.520 g) were added. The reaction mixture was stirred at room temperature for 5 minutes under an argon atmosphere, then the heat block was set at 50° C., and the reaction mixture was stirred at 50° C. for 6 hours, then at room temperature over the weekend. The reaction mixture was diluted with water (approximately 200 mL) and then extracted with ethyl ether (3 x 100 mL). The combined ether layers were washed with saturated _aqueous NaHCO (50 mL), brine (50 mL), dried over _MgSO , filtered and evaporated to dryness in vacuo. A pale yellow oil (4.166 g, 114% yield) was obtained. NMR shows it to be a mixture of desired product and starting bromoglycol, estimated to be about 57% product). This was used in the next step without further purification. MS (APCI): Calcd for _C19H31BO6 ( _M +H) ₌ 367; Found: 367. ¹ H NMR (400 MHz, methanol-d ₄ ) δ 7.69-7.63 (m, 2H), 6.95-6.90 (m, 2H), 4.18-4.11 (m, 2H) , 3.86-3.82 (m, 2H), 3.72-3.67 (m, 2H), 3.66-3.60 (m, 2H), 3.54-3.48 (m, 4H), 3.34(s, 3H).

Compound PLC-17.2

A 500 mL 2N round bottom flask was placed in an aluminum heat block and equipped with a stir bar. The flask was equipped with a finned condenser/gas adapter, a stopper, and a flow control valve. The system was flushed with argon. Add 6-bromo-1H,3H-benzo[de]isochromene-1,3-dione (60.0 mmol, 16.626 g) and 4-bromo-2-nitrophenol (120.0 mmol, 26.160 g) to the flask. , followed by the addition of anhydrous NMP (250 mL). NaOH (30.0 mmol, 1200 mg) and copper (powder) (30.0 mmol, 1907 mg) were added to the flask, followed by anhydrous NMP (250 mL). The flask was stirred under an argon atmosphere, the heat block was set at 170° C., and the reaction was stirred at this temperature for 6 hours and then at room temperature overnight. The room temperature reaction was quenched with an aqueous solution of 1N HCl (60 mL). The reaction mixture was transferred to a 2 L Erlenmeyer flask and diluted with water to a total volume of about 1100 mL while stirring vigorously. The slurry was stirred at room temperature for 1 hour, then the precipitate was filtered off and washed with water. The crude product was sucked dry for approximately 10 minutes, then suspended in methanol (approximately 350 mL) and stirred at room temperature for 45 minutes. The precipitate was filtered off and pulled dry for about 10 minutes, then the precipitate was suspended in acetone (120 mL) and stirred at room temperature for 45 minutes. The precipitate was filtered off and washed with a small amount of acetone. The precipitate was dried by suction for about 30 minutes and then dried in a vacuum oven at about 110° C. overnight. 16.54 g (67% yield) of light brown powder was obtained. MS (APCI): Calcd for _C18H8BrNO6 ( _M +H) ₌ 414; Found: 414. ^1H NMR (400MHz, DMSO- _d6 ) δ 8.75 (dd, J=8.4, 1.1Hz, 1H), 8.63 (dd, J=7.3, 1.1Hz, 1H), 8.50 (d, J=2.4Hz, 1H), 8.44 (d, J=8.2Hz, 1H), 8.12 (dd, J=8.8, 2.5Hz, 1H), 7 .99 (dd, J = 8.5, 7.3 Hz, 1H), 7.61 (d, J = 8.8 Hz, 1H), 7.18 (d, J = 8.3 Hz, 1H).

Compound PLC-17.3

A 1 L 3N round bottom flask was placed in an aluminum heat block and equipped with a stir bar. The flask was equipped with a finned condenser/gas adapter, a stopper, and a flow control valve. The system was flushed with argon. In a flask, PLC-17.2 (26.37 mmol, 10.923 g), SnCl ₂ 2H ₂ O (105.5 mmol, 23.799 g), and HCl (4.0 N, 263.7 mmol, 65.9 mL), Subsequently, 2MeTHF (185 mL) was added. The reaction mixture was stirred under argon and the heat block was set at 90°C. The reaction mixture was stirred at 90° C. for 30 minutes and then cooled to room temperature. The mixture was stirred and titrated to pH ˜8 with aqueous 2N NaOH. The tin salts were removed by filtration and the filter cake was washed with 2MeTHF (6 x 50 mL). The aqueous layer was treated with NaCl until saturation, then the layers were separated. The aqueous layer was extracted with 2MeTHF (2 x 50 mL), then the combined 2MeTHF layers were dried over _MgSO4 , filtered and evaporated to dryness in vacuo, followed by solids in a vacuum oven at ~110 °C overnight. Dry. 9.444 g (93% yield) was obtained. MS ₍ APCI): Calcd for _C18H10BrNO4 (M+H) = ₃₈₄ ; Found: 384. ¹ H NMR (400 MHz, tetrachloroethane-d ₂ ) δ 8.86 (dd, J=8.4, 1.2 Hz, 1H), 8.68 (dd, J=7.3, 1.2 Hz, 1H) , 8.48 (d, J = 8.3 Hz, 1H), 7.89 (dd, J = 8.4, 7.3 Hz, 1H), 7.11 (d, J = 2.1 Hz, 1H), 7.03-6.91 (m, 3H).

Compound PLC-17.4

A stir bar was placed in a 100 mL collection flask. _NaNO2 (154.9 mmol, 10.688 g) and water (45 mL) were added to the flask. The flask was stirred at 0°C in an ice water bath. A stir bar was placed in another 500 mL collection flask. PLC-17.3 (20.65 mmol, 7.933 g), acetic acid (150 mL), and concentrated HCl (12.1N, 103.2 mmol, 8.6 mL) were added to the flask. The mixture was stirred at room temperature for 5 minutes and then cooled in an ice water bath at 0° C. for about 1 minute. Immediately began adding the solution of _NaNO2 . The addition took place over approximately 15 minutes. The crude diazo solution was stirred at 0°C for 1 hour. While stirring the diazo solution, a 1 L 3N round bottom flask was placed in an aluminum heat block equipped with a large stir bar and finned condenser. To the flask were added CuSO ₄ .5H ₂ O (140.4 mmol, 35.059 g) and water (420 mL). The mixture was stirred at room temperature. Approximately 15 minutes before the diazo solution was finished, the _CuSO4 solution was heated to 130 °C. With high speed stirring, the diazo solution was added to the _CuSO4 solution using a peristaltic pump and chemically resistant tubing over 45 minutes. Once the addition was complete, the mixture was heated to 130° C. for about 1 minute and then placed in a room temperature water bath to allow the temperature to drop rapidly. The crude product was filtered off and washed with water. The crude precipitate was boiled in methanol (approximately 100 mL), then cooled to 0° C. (ice-water bath), filtered off, and washed with methanol. The crude product was then heated to about 95° C. in toluene (about 75 mL), then cooled to 0° C. (ice-water bath) and then left overnight to reach room temperature. The precipitate was filtered off and washed with a small amount of toluene. The crude product was dried by suction and then in a vacuum oven at about 110°C. 5.538 g (73% yield) of a yellowish solid was obtained. MS ₍ APCI): Calcd for _C18H7BrO4 (M+H) = ₃₆₇ ; Found: 367. ¹ H NMR (400 MHz, tetrachloroethane-d ₂ ) δ 8.61 (d, J = 7.9 Hz, 1H), 8.58 (d, J = 8.4 Hz, 1H), 8.19 (d, J = 2.2Hz, 1H), 7.94 (d, J = 8.0Hz, 1H), 7.69 (dd, J = 8.8, 2.3Hz, 1H), 7.35 (s, 0H) , 7.31 (d, J=8.8Hz, 1H).

Compound PLC-17.5

A 100 mL 2N round bottom flask was placed in an aluminum heat block and equipped with a stir bar. The flask was fitted with a finned condenser/gas adapter and a flow control valve. The system was flushed with argon. In a flask were added PLC-17.4 (0.702 mmol, 250 mg), 2-(4-aminophenyl)acetic acid (1.754 mmol, 265 mg), and DMAP (0.0512 mmol, 6.3 mg), followed by anhydrous DMF ( 10 mL) was added. The reaction mixture was stirred under argon and the heat block was set at 170°C. The reaction mixture was stirred at 170° C. for 9 hours and then at room temperature. The crude reaction mixture was diluted with 75 mL of water. The mixture was stirred for 5 minutes, then the crude product was filtered off and dried under suction for 5 minutes. The wet precipitate was dried in a vacuum oven at approximately 110° C. overnight. 366 mg (107% yield) of yellowish powder was obtained. NMR shows about 10%-15% dimethylamide byproduct. MS ( _APCI ): Calcd for _C26H14BrNO5 (M+H) = ₅₀₀ ; Found: 500. ¹ H NMR (400 MHz, DMSO-d ₆ ) δ 8.60 (d, J=2.3 Hz, 1H), 8.49-8.45 (m, 2H), 8.39 (d, J=8. 1Hz, 1H), 7.80-7.75 (m, 1H), 7.48-7.43 (m, 2H), 7.43-7.38 (m, 2H), 7.31-7. 27 (m, 2H), 3.67 (s, 2H).

Compound PLC-17.6

A 250 mL 2N round bottom flask was placed in an aluminum heat block and equipped with a stir bar. The flask was fitted with a finned condenser/gas adapter and a flow control valve. The system was flushed with argon. In a flask, compound PLC-17.5 (2.00 mmol, 1001 mg), compound 17.1 (4.00 mmol, 1465 mg), K ₂ CO ₃ (5.50 mmol, 760 mg), and Pd(dppf)Cl ₂ (0 .140 mmol, 102 mg) was added, followed by THF (60 mL), DMF (12 mL), and water (6 mL). The reaction mixture was stirred under argon and sparged with nitrogen for 10 minutes. The nitrogen sparge was stopped and stirring continued under argon. The heat block was set at 80°C for 2 hours. The 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): Calcd for _C39H33NO9 ( _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-17

A stir bar was placed in a 40 mL vial, followed by PLC-17.6 (0.075 mmol, 49.5 mg), PLC-1.1-diethyl 5,5-difluoro-10-(4-hydroxy-2,6-dimethyl phenyl)-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-di Carboxylate (0.050 mmol, 25.6 mg), DMAP.pTsOH salt (0.100 mmol, 29.4 mg), and EDC.HCl (0.200 mmol, 38.3 mg) were charged followed by anhydrous DCM. The vial was capped and the reaction mixture was stirred at room temperature overnight. The crude reaction was quenched with a few drops of TFA and loaded onto approximately 65 g of flash silica gel in a loader. Purified by silica gel flash chromatography (120 g, solids, equilibrated in 100% DCM, elution 100% DCM (3 CV) → 10% EtOAc/DCM (10 CV) → 40% EtOAc/DCM (10 CV)). Fractions containing product were evaporated to dryness in vacuo. The crude product was dried in a vacuum oven at about 110°C. Obtained 52 mg (90% yield) of an orange solid. MS (APCI): Calcd for C ₆₆ H ₆₂ BF ₂ N ₃ O ₁₃ (M-) = 1153; Found: 1153. ¹ H NMR (400 MHz, tetrachloroethane-d ₂ ) δ 8.68 (d, J = 7.9 Hz, 1H), 8.63 (d, J = 8.4 Hz, 1H), 8.25 (d, J = 2.1Hz, 1H), 8.11 (d, J = 8.2Hz, 1H), 7.78 (dd, J = 8.6, 2.1Hz, 1H), 7.68 to 7.61 ( m, 4H), 7.50 (d, J = 8.6Hz, 1H), 7.43 to 7.35 (m, 3H), 7.12 to 7.07 (m, 2H), 7.05 ( s, 2H), 4.28 (q, J = 7.1Hz, 4H), 4.22 (t, J = 4.8Hz, 2H), 4.01 (s, 2H), 3.90 (t, J=4.8Hz, 2H), 3.78 to 3.73 (m, 2H), 3.72 to 3.62 (m, 4H), 3.59 to 3.54 (m, 2H), 3. 38 (s, 3H), 2.84 (s, 6H), 2.16 (s, 6H), 1.74 (s, 6H), 1.34 (t, J=7.1Hz, 6H).

Synthesis of compound PLC-18

Compound PLC-18.1

A 50 mL 2N round bottom flask was placed in an aluminum heat block and equipped with a stir bar. The flask was equipped with a finned condenser/gas adapter, a stopper, and a flow control valve. The system was flushed with argon. To the flask were added PLC-6.3 (3.00 mmol, 1101 mg), ethanolamine (12.0 mmol, 0.725 mL), and DMAP (0.900 mmol, 110 mg), followed by anhydrous DMF (8 mL). The reaction mixture was stirred under argon and the heat block was set at 165°C. The reaction mixture was stirred at this temperature for 3 hours, then the reaction mixture was cooled to room temperature. The solvent was evaporated to dryness in vacuo. The residue was triturated with water (50 mL) and 6N aqueous HCL (10 mL). The mixture was sonicated for several minutes and then stirred at room temperature for 30 minutes, then the solid product was filtered off and washed with water. The crude filter cake was dried in a vacuum oven at about 110° C. overnight. Obtained 1.038 g (84% yield) of a dark brown solid. MS ( _APCI ): Calcd for _C20H12BrNO4 (M+H) = ₄₁₀ ; Found: 410.

Compound PLC-18.2

PLC-18.2 was treated with PLC-18.1 (2.531 mmol) in THF/DMF/H ₂ O (60 mL/12 mL/6 mL) at 80° C. for 30 min in a similar manner to PLC-17.6. , 1.038 g), (4-(trifluoromethyl)phenyl)boronic acid (5.062 mmol, 961 mg), K ₂ CO ₃ (6.960 mmol, 962 mg), and Pd(dppf)Cl ₂ (0.177 mmol, 130mg). The crude product was precipitated by adding water (100 mL) and the resulting solid was then filtered off and washed with water. The crude product was triturated with methanol and then dried in a vacuum oven at about 110° C. overnight. 1.017 g (84% yield) was obtained. MS ₍ APCI): Calcd for _C27H16F3NO4 (M+H) _{= 476} ; Found: 476. ^1H NMR (400MHz, TCE) δ 8.66 (d, J = 7.8Hz, 1H), 8.61 (d, J = 8.3Hz, 1H), 8.25 (d, J = 2.2Hz , 1H), 8.06 (d, J = 8.0Hz, 1H), 7.83 to 7.75 (m, 5H), 7.52 (d, J = 8.6Hz, 1H), 7.37 (d, J=8.4Hz, 1H), 4.45 (t, J=5.2Hz, 2H), 3.98 (q, J=5.3Hz, 2H), 2.49 (t, J= 5.5Hz, 1H).

Compound PLC-18.3

A 250 mL 2N round bottom flask was placed in an aluminum heat block and equipped with a stir bar. The flask was fitted with a finned condenser/gas adapter, a stopper, and a flow control valve. The system was flushed with argon. Add PLC-18.2 (2.124 mmol, 1.01 g), pTsCl (6.372 mmol, 1.215 g), anhydrous DMF (20 mL), and Et ₃ N (6.372 mmol, 0.888 mL) to the flask. Ta. The reaction mixture was stirred under argon and heated to 80° C. for 2 hours. An unexpected reaction occurred when tosylate was replaced in situ by chloride ions. The reaction mixture was cooled to room temperature and diluted with water (100 mL). The crude product was filtered off and washed with water. The crude product was triturated with MeOH. The product was dried in a vacuum oven at about 110° C. overnight. Obtained 974 mg of an orange solid (93% yield). MS ₍ APCI): Calcd _{for C27H15ClF3NO3} (M+ _H ) = 494; Found: 494. ^1H NMR (400MHz, TCE) δ 8.67 (d, J = 7.9Hz, 1H), 8.62 (d, J = 8.3Hz, 1H), 8.27 (d, J = 2.2Hz , 1H), 8.08 (d, J = 7.9Hz, 1H), 7.86 to 7.73 (m, 5H), 7.53 (d, J = 8.6Hz, 1H), 7.39 (d, J = 8.4 Hz, 1H), 4.56 (t, J = 6.9 Hz, 2H), 3.87 (t, J = 6.8 Hz, 2H).

Compound PLC-18.4

A 100 mL 2N round bottom flask was placed in an aluminum heat block and equipped with a stir bar. The flask was equipped with a finned condenser/gas adapter, a stopper, and a flow control valve. PLC-18.3 (0.607 mmol, 300 mg), 4-hydroxy-2,6-dimethylbenzaldehyde (1.336 mmol, 201 mg), and K ₂ CO ₃ (1.215 mmol, 168 mg) were added to the flask, followed by Then anhydrous DMF (20 mL) was added. The reaction mixture was stirred under argon and the heat block was set at 100°C. The reaction mixture was stirred under an argon atmosphere for 8 hours and then at room temperature overnight. The crude reaction mixture was diluted with water (approximately 100 mL) and the precipitate was filtered off and washed with water. The crude product was dissolved in DCM and evaporated to dryness. The crude product was redissolved in DCM and evaporated onto flash silica gel (~20g). Silica gel flash chromatography (120 g, solid content, equilibration 70% hexane/DCM, elution 70% hexane/DCM (2 CV) → 100% DCM/hexane (10 CV) → isocratic 100% DCM/hexane (5 CV) → 0 %EtOAc/DCM (0CV)→isocratic 0%EtOAc/DCM (10CV)→40%EtOAc/DCM (40CV)). Fractions containing product were evaporated to dryness in vacuo. 48 mg (13% yield) of a yellow solid was obtained. MS (APCI): Calcd for C ₃₆ H ₂₄ F ₃ NO ₀ (M-) = 607; Found: 607. ^1H NMR (400MHz, TCE) δ 10.41 (s, 1H), 8.69 (d, J=7.8Hz, 1H), 8.64 (d, J=8.3Hz, 1H), 8. 27 (d, J = 2.1Hz, 1H), 8.09 (d, J = 8.1Hz, 1H), 7.85 to 7.75 (m, 5H), 7.53 (d, J = 8 .6Hz, 1H), 7.39 (d, J = 8.3Hz, 1H), 6.66 (s, 2H), 4.65 (t, J = 6.2Hz, 2H), 4.38 (t , J=6.2Hz, 2H), 2.57(s, 6H).

Compound PLC-18

A 100 mL 2N round bottom flask was placed in an aluminum heat block and equipped with a stir bar. The flask was equipped with a finned condenser/gas adapter, a stopper, and a flow control valve. The system was flushed with argon. To a flask were added PLC-18.4 (0.0741 mmol, 45 mg), ethyl 2,4-dimethyl-1H-pyrrole-3-carboncarboxylate (0.1556 mmol, 26 mg), followed by anhydrous DCE (15 mL). added. The reaction mixture was sparged with nitrogen for 10 minutes under an argon atmosphere. Several small granules of pTsOH.H ₂ O were collected at the end of the spatula and dipped into the reaction mixture. Stirring and nitrogen sparging were continued for an additional 5 minutes. The nitrogen sparge was stopped and the reaction mixture was stirred under an argon atmosphere. The heat block was set at 85° C. and the reaction mixture was stirred at this temperature overnight. TLC shows complete conversion to the desired dipyrrolomethane. The reaction mixture was cooled to room temperature in a water bath. DDQ (0.111 mmol, 25 mg) was added to the flask and the reaction mixture was stirred at room temperature for 1 hour. TLC shows complete oxidation to dipyrromethene. Et ₃ N (0.593 mmol, 0.139 mL) and BF ₃ .OEt ₂ (0.110 mmol, 0.111 mL) were added to the flask. The addition of both reagents was repeated after 2 minutes, then the heat block was set at 60° C. and the reaction mixture was stirred at this temperature under argon for 2 hours. The crude BODIPY was loaded directly onto flash silica gel (approximately 25 g). Silica gel flash chromatography (80 g, solid content, equilibration 80% DCM/hexane, elution 50% DCM/hexane (2 CV) → 100 DCM/hexane (10 CV) → isocratic 100% DCM/hexane (10 CV) → 0% Purified by EtOAc/DCM (0CV) → isocratic 0% EtOAc/DCM (5CV) → 40% EtOAc/DCM (40CV). Fractions containing product were evaporated to dryness in vacuo. Obtained 50 mg (70% yield) of an orange solid. MS ₍ APCI) _: Calcd _{for C54H45BF5N3O8 (} M- ₎ = 969; Found: 969. ^1H NMR (400MHz, TCE) δ 8.70 (d, J = 7.9Hz, 1H), 8.65 (d, J = 8.4Hz, 1H), 8.28 (d, J = 2.2Hz , 1H), 8.09 (d, J = 8.1Hz, 1H), 7.85 to 7.75 (m, 5H), 7.53 (d, J = 8.6Hz, 1H), 7.40 (d, J=8.3Hz, 1H), 6.78 (s, 2H), 4.67 (t, J=6.3Hz, 2H), 4.36 (t, J=6.4Hz, 2H) , 4.25 (q, J=7.1Hz, 4H), 2.81 (s, 6H), 2.05 (s, 6H), 1.67 (s, 6H), 1.32 (t, J =7.1Hz, 6H).

Synthesis of compound PLC-19

Compound PLC-19.1

In a flask were added PLC-6.3 (1.5 g, 4.1 mmol), 2-(2-aminoethoxy)ethane-1-ol (859.0 mg, 8.2 mmol) and DMAP (35 mmol) in DMF (30 ml). .1 mg, 0.3 mmol) was degassed at room temperature. The reaction mixture was heated to 165°C and the reaction was held at this temperature for 2 hours. TLC and LCMS showed the reaction was complete. The reaction was cooled to room temperature. _H2O (70ml) was added to precipitate the product. The precipitate was collected by filtration. The solid was washed with H ₂ O (150 ml) and further dried in a vacuum oven at 100° C. for 3 hours to give PLC-19.1 as a yellow solid for the next step without further purification. 1.45g, 78% yield. MS (APCI): Calcd for C ₂₂ H ₁₆ BrNO ₅ ([MH] ^- ) = 454; Found: 454. ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) 8.62 (d, J = 8.0 Hz, 1H), 8.59 (d, J = 8.0 Hz, 1H), 8.19 (d, J = 2 .4Hz, 1H), 7.92 (d, J=8.0Hz, 1H), 7.65 (dd, J=8.0Hz, J=2.4Hz, 2H), 7.33 (d, J= 8.0Hz, 1H), 7.29 (d, J = 8.0Hz, 1H), 4.42 (t, J = 5.6Hz, 2H), 3.85 (t, J = 5.6Hz, 2H) ), 3.67 (m, 4H).

Compound PLC-19.2

A 250 mL flask was equipped with a stir bar. In a flask were added PLC-19.1 (800.0 mg, 1.8 mmol), 4-(trifluoromethyl)phenylboronic acid (670 mg) in THF/DMF/H ₂ O (48 ml/9.6 ml/4.8 ml). .0 mg, 3.5 mmol), Pd(dppf) _Cl2 (90.6 mg, 0.1 mmol) and _K2CO3 ( _659.5 mg, 4.8 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 H ₂ O (150 ml) which was added to precipitate the product. The precipitate was collected by filtration. The solid was washed with H ₂ O (200 ml) and MeOH (20 ml) and further dried in a vacuum oven at 100° C. for 3 hours to give PLC-19.2 as a yellow-green solid for the next step without further purification. I got it. Quantitative yield. MS ₍ APCI): Calcd for _{C29H20F3NO5 (} [M+H] ⁺ ) = 520; Found: ₅₂₀ . ^1H NMR (400MHz, _CDCl2CDCl2 ) 8.67 (d, J=8.0Hz, _1H ), 8.61 (d, J=8.0Hz, 1H), 8.26 (d, J=2 .0Hz, 1H), 8.07 (d, J = 8.0Hz, 1H), 7.79 (m, 5H), 7.52 (d, J = 8.4Hz, 1H), 7.38 (d , J=8.4Hz, 1H), 5.11 (bs, 1H), 4.44 (t, J=1.6Hz, 2H), 3.86 (t, J=1.6Hz, 2H), 3 .68 (m, 4H).

Compounds PLC-19.3A and PLC-19.3B

A 100 mL flask was equipped with a stir bar. PLC-19.2 (900.0 mg, 1.7 mmol) and DMF/THF (18 ml/6 ml) were added to the flask. The solution was degassed at room temperature. Methanesulfonyl chloride (595.4 mg, 5.2 mmol) and TEA (526.2 mg, 5.2 mmol) were added. The solution was then heated to 90°C and held at this temperature for 20 minutes. The reaction was monitored using TLC. After completion, the reaction was worked up by addition of H ₂ O (150 ml) which was added to precipitate the product. The precipitate was collected by filtration. The solid was washed with H ₂ O (100 ml) and MeOH (15 ml) and further dried in a vacuum oven at 100° C. for 3 hours to give PLC-19. as a yellow solid for the next step without further purification. A mixture of 3A and PLC-19.3B was obtained. Quantitative yield. For PLC-19.3A, MS (APCI): Calculated value of C ₃₀ H ₂₂ F ₃ NO ₇ S ([M+H] ⁺ )=598; Actual value: 598. ^1H NMR (400MHz, _CDCl2CDCl2 ) 8.65 (d, J=8.0Hz, _1H ), 8.60 (d, J=8.0Hz, 1H), 8.26 (d, J=2 .0Hz, 1H), 8.07 (d, J = 8.0Hz, 1H), 7.78 (m, 5H), 7.52 (d, J = 8.4Hz, 1H), 7.38 (d , J=8.4Hz, 1H), 4.44 (t, J=2.0Hz, 2H), 4.35 (m, 2H), 3.86 (t, J=2.0Hz, 2H), 3 .81 (m, 2H), 3.01 (s, 3H). For PLC-19.3B, MS (APCI): Calculated value for C ₂₉ H ₁₉ ClF ₃ NO ₄ ([MH] ^- ) = 537; Actual value: 537. ^1H NMR (400MHz, _CDCl2CDCl2 ) 8.66 (d, J=8.0Hz, _1H ), 8.61 (d, J=8.0Hz, 1H), 8.26 (d, J=2 .0Hz, 1H), 8.07 (d, J = 8.0Hz, 1H), 7.79 (m, 5H), 7.52 (d, J = 8.4Hz, 1H), 7.37 (d , J=8.4Hz, 1H), 4.43 (t, J=2.0Hz, 2H), 3.86 (t, J=2.0Hz, 2H), 3.81 (t, J=1. 6Hz, 2H), 3.63 (t, J=1.6Hz, 2H).

Compound PLC-19.4

NaH (15.4 mg, 0.4 mmol) and DMF (5 ml) were added to a 100 ml flask, followed by 4-hydroxy-2,6-methylbenzaldehyde (43.6 mg, 0.3 mmol). The mixture was kept stirring at room temperature for 10 minutes. PLC-19.3B (104.0 mg, 0.2 mmol) was added. The reaction was heated to 160° C. and kept stirring at this temperature overnight. TLC (50% EtOAc in hexanes) showed completion of the reaction. The reaction mixture was purified by silica gel flash chromatography using EtOAc in DCM (0%→40%) as eluent to give pure compound PLC-19.4 as an orange solid (73.0 mg, 59% yield). ) was obtained. MS ₍ APCI): Calcd for _{C38H28F3NO6 (} [M+H] ⁺ ) = 652; Found: ₆₅₂ . ^1H NMR (400MHz, _CDCl2CDCl2 ) δ 10.20 (s, _1H ), 8.61 (d, J=8.0Hz, 1H), 8.56 (d, J=8.0Hz, 1H) , 8.22 (d, J=2.0Hz, 1H), 8.00 (d, J=8.0Hz, 1H), 7.81 (m, 5H), 7.50 (d, J=8. 0Hz, 1H), 7.32 (d, J = 8.0Hz, 1H), 6.56 (s, 2H), 4.44 (t, J = 2.0Hz, 2H), 4.00 (m, 2H), 3.92 (t, J=2.0Hz, 2H), 3.86 (m, 2H), 2.45 (s, 6H).

Compound PLC-19

A 100 mL two neck round bottom flask was fitted with an air condenser and a stir bar. PLC-19.4 (73.0 mg, 0.1 mmol) and ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (39.0 mg, 0.2 mmol) were added to the flask, followed by anhydrous dichloroethane (7 ml). ) was added. The reaction mixture was sparged with Ar for 30 min, then p-TsOH.H ₂ O (0.7 mg, 0.006 mmol) was added. The reaction solution was heated to 85°C and kept at this temperature overnight. The reaction was then cooled to room temperature and DDQ (13.7 mg, 0.06 mmol) was added. The reaction was held at room temperature for 30 minutes. Then BF ₃ .OEt ₂ (0.16 mL, 1.3 mmol) and Et ₃ N (0.12 mL, 0.9 mmol) were added at room temperature. The reaction mixture was heated to 60°C and held at this temperature for 1 hour. The reaction mixture was loaded onto silica gel and purified by flash chromatography using EtOAc in DCM (0%→10%) as eluent to give pure PLC-19 as an orange solid (38.0 mg, 36% yield). ) was obtained. MS (APCI): Calculated for C ₅₆ H ₄₉ BF ₅ N ₃ O ₉ ([MH] ^- ) = 1013; Found: 1013. ^1H NMR (400MHz, _CDCl2CDCl2 ) 8.68 (d, J=8.0Hz, _1H ), 8.63 (d, J=8.0Hz, 1H), 8.27 (d, J=2 .4Hz, 1H), 8.08 (d, J = 8.0Hz, 1H), 7.79 (m, 5H), 7.52 (d, J = 8.0Hz, 1H), 7.38 (d , J=8.0Hz, 1H), 6.69 (s, 2H), 4.48 (t, J=6.0Hz, 2H), 4.26 (q, J=7.2Hz, 4H), 4 .14 (m, 2H), 3.92 (m, 4H), 2.82 (s, 6H), 2.05 (s, 6H), 1.70 (s, 6H), 1.33 (t, J=7.2Hz, 6H).

Compound PLC-20

Compound PLC-20.2

PLC-20.1 (1.223 g, 3.33 mmol, 1 eq.) was suspended in 35 mL of anhydrous DMSO and reacted with 5-amino-1-pentanol (0.687 g, 6.66 mmol, 2 eq.) at room temperature. Added to the 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 was filtered, washed with water (250 mL), then MeOH (100 mL), and dried in a vacuum oven to yield 1.2 g of a greenish yellow solid (85% yield). Ta. MS ₍ APCI): Calcd for _C23H18BrNO4 ( _M- ) = 453; Found: 453. 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-20.3

PLC-20.2 (1.13 g, 2.5 mmol, 1 eq) was suspended in DMF (10 ml), H ₂ O (5 ml) and 4-(trifluoromethyl)benzeneboronic acid (0.949 g, 5 .0 mmol, 2 eq.), _K2CO3 (0.691 _g , 5.0 mmol, 2 eq.), Pd(dppf) _Cl2.DCM (40.8 mg, 0.05 mmol, 0.02 eq.) were 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): Calcd for _C30H22F3NO4 ( _M- ) ₌ 517; Found: 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-20.4

Reflux a mixture of PLC-20.3 (0.66 g, 1.288 mmol) and 48% aqueous HBr (20.0 ml) in a heat block at 120 °C for 5 h with stirring (HBr 48% bp: 126 °C). did. 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): Calcd _{for C30H21BrF3NO3 ( M-} ) = 581; Found: 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-20.5

2,6-dimethyl-4-hydroxybenzaldehyde (60.08 mg, 0.4 mmol, 1 eq.), K ₂ CO ₃ (110.56 mg, 0.8 mmol, 2 eq.), NaI in anhydrous DMF (4.0 ml). (4.6 mg, catalytic amount) and PLC-20.4 (243.76 mg, 0.42 mmol, 1.05 eq.) was sonicated for 10 min before stirring at 65 °C for 24 h under an argon atmosphere. Mixed by processing. After cooling to room temperature, the mixture was concentrated to dryness, washing the solid with hot water (50 ml x 2) and collecting the yellow solid by filtration. The crude material was sonicated with MeOH at 65°C, cooled, filtered, and dried in a vacuum oven. The product was used in the next step without further purification, giving 257 mg, 98% yield. MS ₍ APCI): Calcd for _C39H30F3NO5 ( _M- ) ₌ 649; Found: 649. ¹ H NMR (400MHz,) δ 10.33 (s, 1H), 8.56 (d, J = 7.8Hz, 1H), 8.51 (d, J = 8.4Hz, 1H), 8.17 (d, J=2.2Hz, 1H), 7.98 (d, J=8.0Hz, 1H), 7.69 (dd, J=9.0, 1.9Hz, 5H), 7.43 ( d, J = 8.6Hz, 1H), 7.28 (d, J = 8.3Hz, 1H), 6.51 (s, 2H), 4.11 (t, J = 7.6Hz, 3H), 3.94 (t, J=6.4Hz, 2H), 2.50 (s, 6H), 1.76 (dt, J=24.1, 7.8Hz, 4H).

Compound PLC-20

Step 1: In a 50 ml vial (equipped with septum cap, magnetic stirring bar), compound benzyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (68. 55 mg, 0.41 mmol, 2.05 eq.), PLC-20.5 (129.93 mg, 0.2 mmol, 1 eq.) was bubbled with argon, stirred at room temperature for 15 min, and mixed with 50 ml DCE + 5 drops of TFA. 1 ml of the mixture was added at once. The resulting mixture was then stirred at 68° C. for 24 hours under an argon atmosphere. LCMS showed only 50% starting material was consumed. 8 mg of pTSA was added and the RX was further stirred at 90° C. for 45 minutes, and LCMS showed complete conversion of the starting material. The crude product was used in the next step in situ without further purification.

Step 2: The above mixture was cooled to room temperature and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) (0.148 g, 0.625 mmol) was added in one portion. The resulting mixture was stirred at room temperature for 1/2 hour. TLC and LCMS showed complete conversion of starting material.

Step 3: The above mixture was cooled to 0°C and then stirred with triethylamine (0.25ml, 3.48mmol) for 15 minutes. BF ₃ etherate (071 mL, 2.76 mmol) was added dropwise. The resulting reaction mixture was stirred at 86° C. for 45 min under an argon atmosphere, cooled to 0° C., quenched with EtOH (2 ml) and the solvent was removed by rotary evaporation. The residue was chromatographed on a column of silica gel (80 g) eluting with DCM only (1 CV) then DCM/EtOAc (98:2), then washed with EtOH to give the pure title product (1574-114). was obtained as an orange-yellow solid (0.120 g, 59% overall yield based on 1574-112 aldehyde SM). MS (APCI): Calcd. (M-) for C ₅₇ H ₅₁ BF ₅ N ₃ O ₈ = 1011; Found: 1011. ¹ H NMR (400 MHz,) δ 8.57 (d, J = 7.9 Hz, 1H), 8.52 (d, J = 8.3 Hz, 1H), 8.17 (d, J = 2.3 Hz, 1H), 7.98 (d, J = 8.0Hz, 1H), 7.69 (dd, J = 9.5, 1.8Hz, 5H), 7.42 (d, J = 8.6Hz, 1H ), 7.28 (d, J=8.3Hz, 1H), 6.65 (s, 2H), 4.18 (q, J=7.1Hz, 4H), 4.12 (t, J=7 .6Hz, 2H), 3.93 (t, J = 6.5Hz, 2H), 2.73 (s, 6H), 1.99 (s, 6H), 1.8 2 (t, J = 7. 3Hz, 2H), 1.79 to 1.69 (m, 2H), 1.64 (s, 6H), 1.56 (s, 2H), 1.24 (t, J = 7.1Hz, 6H) . 2.28-2.19 (m, 4H), 2.06-1.85 (m, 4H), 0.78 (d, J=14.2Hz, 2H).

Compound PLC-21

Compound PLC-21.1

PLC-20.1 (1.223 g, 3.33 mmol, 1 eq.) was suspended in 35 mL of anhydrous DMSO and reacted with 5-amino-1-pentanol (0.687 g, 6.66 mmol, 2 eq.) at room temperature. Added to the mixture. The resulting mixture was stirred at 160° C. for 3 days, 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 (92% yield). I got it. MS ₍ APCI): Calcd for _C23H18BrNO4 ( _M- ) = 425; Found: 425. ^1H NMR (400MHz) δ 8.56 (d, J = 7.9Hz, 1H), 8.52 (d, J = 8.4Hz, 1H), 8.13 (d, J = 2.3Hz, 1H ), 7.86 (d, J = 7.9Hz, 1H), 7.57 (dd, J = 8.8, 2.3Hz, 1H), 7.26 (d, J = 8.4Hz, 1H) , 7.22 (d, J = 8.8 Hz, 1H), 4.24 (t, J = 6.1 Hz, 2H), 3.48 (q, J = 6.1 Hz, 2H), 3.06 ( t, J = 6.9Hz, 1H), 1.95 to 1.83 (m, 2H).

Compound PLC-21.2

PLC-21.1 (1.06 g, 2.5 mmol, 1 eq) was suspended in DMF (10 ml), H ₂ O (5 ml) and 4-(trifluoromethyl)benzeneboronic acid (0.949 g, 5 .0 mmol, 2 eq.), _K2CO3 (0.691 _g , 5.0 mmol, 2 eq.), Pd(dppf) _Cl2.DCM (40.8 mg, 0.05 mmol, 0.02 eq.) were 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 1.04 g of a greenish yellow solid (85% yield). MS ₍ APCI): Calcd for _C30H22F3NO4 ( _M- ) ₌ 517; Found: 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-21.3

A mixture of PLC-21.2 (1.6 g, 3.2 mmol) and 48% aqueous HBr (30.0 ml) was heated to reflux with stirring in a heat block at 130° C. for 3 days. The same amount of 48% aqueous HBr was added twice more over the next two days, totaling 90 ml. 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. 1.7 g of a greenish yellow solid (96% yield) was obtained. The product was used in the next step without further purification. MS ₍ APCI): Calcd _{for C30H21BrF3NO3 ( M-} ) = 551; Found: 551. ^1H NMR (400MHz) δ 8.55 (d, J = 7.9Hz, 1H), 8.50 (d, J = 8.4Hz, 1H), 8.15 (d, J = 2.2Hz, 1H ), 7.96 (d, J = 8.0 Hz, 1H), 7.70 (s, 5H), 7.41 (d, J = 8.6 Hz, 1H), 7.27 (d, J = 8 .3Hz, 1H), 4.22 (t, J=7.1Hz, 2H), 3.45 (t, J=6.8Hz, 2H), 2.25 (q, J=6.9Hz, 2H) .

Compound PLC-21.4

2,6-dimethyl-4-hydroxybenzaldehyde (60.08 mg, 0.4 mmol, 1 eq.), K ₂ CO ₃ (110.56 mg, 0.8 mmol, 2 eq.), NaI in anhydrous DMF (4.0 ml). (4.6 mg, catalytic amount) and PLC-21.3 (231.98 mg, 0.42 mmol, 1.05 eq.) was sonicated for 10 min before stirring at 65 °C for 24 h under an argon atmosphere. Mixed by processing. After cooling to room temperature, the mixture was concentrated to dryness, washing the solid with hot water (50 ml x 2) and collecting the yellow solid by filtration. The crude material was sonicated with MeOH at 65°C, cooled, filtered, and dried in a vacuum oven. The product was used in the next step without further purification, giving 239 mg, 96% yield. MS ₍ APCI): Calcd for _C37H26F3NO5 ( _M- ) ₌ 621; Found: 621. ¹ H NMR (400MHz,) δ 10.34 (s, 1H), 8.56 (d, J = 7.7Hz, 1H), 8.51 (d, J = 8.3Hz, 1H), 8.18 (d, J=2.2Hz, 1H), 7.98 (d, J=7.9Hz, 1H), 7.70 (dd, J=7.4, 2.3Hz, 6H), 7.44 ( d, J = 8.6Hz, 1H), 7.29 (d, J = 8.2Hz, 1H), 6.46 (s, 2H), 4.30 (t, J = 7.0Hz, 2H), 4.09 (t, J=5.9Hz, 2H), 2.47 (s, 6H), 2.17 (t, J=6.7Hz, 2H).

Compound PLC-21

Step 1: In a 50 ml vial (equipped with septum cap, magnetic stir bar), compound benzyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (68. 55 mg, 0.41 mmol, 2.05 eq.), PLC-21.4 (124.32 mg, 0.2 mmol, 1 eq.) was bubbled with argon, stirred at room temperature for 15 min, and mixed with 50 ml DCE + 5 drops of TFA. 1 ml of the mixture was added at once. The resulting mixture was then stirred at 68° C. for 24 hours under an argon atmosphere, and LCMS showed that only 50% of the starting material was consumed. 8 mg of pTSA was added and the RX was further stirred at 90° C. for 45 minutes, and LCMS showed complete conversion of the starting material. The crude product was used in the next step in situ without further purification.

Step 2: The above mixture was cooled to room temperature and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) (0.148 g, 0.625 mmol) was added in one portion. The resulting mixture was stirred at room temperature for 1/2 hour. TLC and LCMS showed complete conversion of starting material.

Step 3: The above mixture was cooled to 0°C and then stirred with triethylamine (0.25ml, 3.48mmol) for 15 minutes. BF ₃ etherate (071 mL, 2.76 mmol) was added dropwise. The resulting reaction mixture was stirred at 86° C. for 45 min under an argon atmosphere, cooled to 0° C., quenched with EtOH (2 ml) and the solvent was removed by rotary evaporation. The residue was chromatographed on a column of silica gel (80 g) eluting with DCM only (1 CV) then DCM/EtOAc (98:2), then washed with EtOH to give the pure title product PLC-21 in orange. Obtained as a yellow solid (0.097 g, 49% overall yield based on PLC-21 aldehyde SM). MS ₍ APCI) _: Calcd _{for C55H47BF5N3O8 (} M-) ₌ 983; Found: 983. ^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), 7.98 (d, J = 8.0Hz, 1H), 7.69 (dd, J = 8.8, 2.0Hz, 5H), 7.42 (d, J = 8.6Hz, 1H ), 7.28 (d, J = 8.3Hz, 1H), 6.58 (s, 2H), 4.33 (t, J = 7.1Hz, 2H), 4.18 (q, J = 7 .1Hz, 4H), 4.08 (t, J = 6.2Hz, 2H), 2.73 (s, 6H), 2.19 (t, J = 6.8Hz, 2H), 1.63 (s , 6H), 1.53 (s, 8H), 1.25 (t, J=7.1Hz, 6H).

Synthesis of compound PLC-22

Compound PLC-22.1:
Compound PLC-27.1 (see above) (9-bromo-2-(3-hydroxypropyl)-1H-xanteno[2, 1,9-def]isoquinoline-1,3(2H)-dione) (330 mg, 0.778 mmol), (2,4,6-triisopropylphenyl)boronic acid (290 mg, 1.17 mmol), Pd(PPh ₃ ) ₄ (80 mg, 0.069 mmol), K ₂ CO ₃ (320 mg, 2.32 mmol) was degassed and heated at 90° C. for 24 hours. The resulting mixture was worked up with water and ethyl acetate. The organic phase was collected, loaded onto silica gel and purified by flash chromatography using an eluent of DCM/EA (0%→40% EA). After removing the solvent under reduced pressure, the desired fractions were collected to give a yellow solid (210 mg, 49% yield). LCMS (APCI-): Calcd for _{C36H37NO4 = 547.27} ; Found: 547. ^1H NMR (400MHz, d2-TCE) δ 8.60-8.48 (m, 2H), 7.93-7.76 (m, 2H), 7.45-7.24 (m, 3H), 6.99 (s, 2H), 4.25 (t, J = 6.1Hz, 2H), 4.01 (q, J = 7.2Hz, 2H), 3.47 (t, J = 5.5Hz , 2H), 2.88 (p, J = 6.8Hz, 1H), 2.65 to 2.43 (m, 2H), 1.89 (d, J = 6.2Hz, 2H), 1.24 (d, J = 6.9Hz, 6H), 1.03 (t, J = 7.1Hz, 12H).

Compound PLC-22.2:
To a solution of compound 1612-48 (210 mg, 0.384 mmol) in 20 mL of DCM was added carbon tetrabromide (CBr ₄ , 252 mg, 0.76 mmol), triphenylphosphine (203 mg, 0.77 mmol) at room temperature. . The whole was stirred for 30 minutes. TLC shows the reaction is complete. The mixture was loaded onto silica gel and purified by flash chromatography using an eluent of hexane/DCM (0%→100% DCM). The desired fractions were collected and concentrated under reduced pressure to give a yellow solid (100 mg, 43% yield). LCMS _{( APCI} +): Calcd for _C36H37BrNO3 (M+H): 610.19; Found: 610. ¹ H NMR (400MHz, d2-TCE) δ 8.52 (dd, J=8.1, 2.5Hz, 2H), 8.00-7.72 (m, 2H), 7.45-7.19 (m, 3H), 6.98 (s, 2H), 4.23 (t, J=7.0Hz, 2H), 3.44 (t, J=6.8Hz, 2H), 3.01~2 .80 (m, 1H), 2.69-2.45 (m, 2H), 2.26 (q, J = 6.9Hz, 2H), 1.24 (d, J = 6.9Hz, 6H) , 1.03 (t, J=6.9Hz, 12H).

Compound PLC-22:
A mixture of compound PLC-22.1 (50 mg, 0.082 mmol), compound PLC1.1 (58.5 mg, 0.10 mmol), K ₂ CO ₃ (20.7 mg, 0.15 mmol) in anhydrous DMF was Sonicate for minutes and then heat at 75° C. for 5 hours under an argon atmosphere. The resulting mixture was diluted with 100 mL of DCM, washed with 0.1 N aqueous HCl (50 mL x 2), dried over _MgSO4 , concentrated to 50 mL, then loaded onto silica gel and diluted with DCM/EA (0%→ Purified by flash chromatography using an eluent of 5% EA). The main desired fractions were collected, concentrated and triturated with methanol, followed by filtration to give a dark red solid (70 mg, 76.6% yield). LCMS ( _APCI- ): Calcd _{for C69H60BCl2F2N3O4 :} 1113.40; _{Found :} 1113. ^1H NMR (400MHz, d2-TCE) δ 8.63-8.43 (m, 2H), 8.08-7.72 (m, 4H), 7.46-7.13 (m, 9H), 6.94 (d, J = 31.3Hz, 4H), 6.38 (s, 2H), 4.35 (t, J = 6.8Hz, 2H), 4.12 (t, J = 5.9Hz , 2H), 2.98 to 2.77 (m, 1H), 2.54 (q, J = 6.8Hz, 6H), 2.23 (d, J = 6.0Hz, 6H), 2.04 ~1.89 (m, 4H), 1.23 (d, J=6.9Hz, 6H), 1.02 (dd, J=6.9, 3.5Hz, 12H).

Synthesis of compound PLC-23

Compound PLC-23.2
4-(3-(9-(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xanteno[2,1,9-def]isoquinolin-2(3H)-yl)propoxy )-2,6-Dimethylbenzaldehyde 2,6-dimethyl-4-hydroxybenzaldehyde (30.04 mg, 0.4 mmol, 1 eq) in anhydrous DMF (4.0 ml), K ₂ CO ₃ (55.28 mg, 0 .4 mmol, 2 eq.), NaI (2.3 mg, catalytic amount) and PLC-23.1 (130.2735 mg, 0.21 mmol, 1.05 eq.) at 65° C. for 24 hours under an argon atmosphere. Mix by sonication for 10 minutes before stirring. After cooling to room temperature, the mixture was concentrated to dryness. The residue was washed with hot water (50ml x 2) and the yellow solid was collected by filtration. The solid was then sonicated with MeOH at 65 °C, cooled, filtered, and dried in a vacuum oven, and the product was used in the next step without further purification, giving 135 mg, 85% yield. I got it. MS (APCI): Formula: Calculated for C ₃₈ H ₂₅ F ₆ NO ₅ (M-) = 689; Found: 689. ^1H NMR (400MHz) δ 10.34 (s, 1H), 8.57 (d, J = 7.9Hz, 1H), 8.52 (d, J = 8.3Hz, 1H), 8.16 ( d, J=2.2Hz, 1H), 8.02 (d, J=8.9Hz, 2H), 7.86 (s, 1H), 7.70 (dd, J=8.6, 2.1Hz , 1H), 7.47 (d, J = 8.6Hz, 1H), 7.30 (d, J = 8.3Hz, 1H), 6.46 (s, 2H), 4.30 (t, J =7.1Hz, 2H), 4.09 (t, J = 6.0Hz, 2H), 2.47 (s, 3H), 2.18 (t, J = 6.6Hz, 2H).

Compound PLC-23: Diethyl 10-(4-(3-(9-(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinoline -2(3H)yl)-propoxy)-2,6-dimethylphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4l ⁴ ,5l ⁴ -dipyrrolo[1,2- c:2',1'-f][1,3,2]diazaborinine-2,8-carboxylate

Step 1: In a 50 ml vial (equipped with septum cap, magnetic stir bar), compound benzyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (58. 19 mg, 0.348 mmol, 2.1 eq.), 1643-005 (115 mg, 0.166 mmol, 1 eq.) was bubbled with argon and stirred at room temperature for 15 minutes. 8 mg of pTSA was added and the RX was stirred at 85° C. for 45 minutes, LCMS showed complete conversion of the starting material. The crude product was used in the next step in situ without further purification.

Step 2: The above mixture was cooled to room temperature and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) (0.113 g, 0.498 mmol, 3 eq.) was added in one portion. The resulting mixture was stirred at room temperature for 1/2 hour. TLC and LCMS showed complete conversion of starting material.

Step 3: The above mixture was cooled to 0<0>C and then stirred with triethylamine (0.462ml, 3.48mmol, 3.32mmol, 20eq) for 15 minutes. BF ₃ etherate (1.224 mL, 9.96 mmol, 60 eq.) was added dropwise. The resulting reaction mixture was sonicated for 10 minutes at room temperature under an argon atmosphere, then stirred at 60° C. for 45 minutes, and then at room temperature for 16 hours. After quenching with EtOH (2 ml), the reaction mixture was concentrated by rotary evaporation. The residue was washed with hot water and the crude product was chromatographed on a column of silica gel (80 g) eluting with DCM only (1 CV) then DCM/EtOAc (98:2), then washed with EtOH. , the pure title product (1643-006) was obtained as an orange-yellow solid (105 mg, 60% overall yield based on 1643-005 aldehyde SM). MS (APCI): Chemical formula: Calculated value for C ₅₆ H ₄₆ BF ₈ N ₃ O ₈ (M-) = 689 1051. ; Actual value: 1051. ¹ H NMR (400 MHz) δ 8.59 (d, J = 7.8 Hz, 1 H), 8.52 (d, J = 8.3 Hz, 1 H), 8.17 (d, J = 2.2 Hz, 1 H ), 8.03 (d, J = 8.1 Hz, 1H), 8.00 (d, J = 1.5 Hz, 2H), 7.86 (s, 1H), 7.69 (dd, J = 8 .6, 2.2Hz, 1H), 7.46 (d, J = 8.6Hz, 1H), 7.30 (d, J = 8.3Hz, 1H), 6.59 (s, 2H), 4 .34 (t, J = 7.1Hz, 2H), 4.18 (q, J = 7.1Hz, 4H), 4.08 (t, J = 6.2Hz, 2H), 2.73 (s, 6H), 2.25 to 2.13 (m, 2H), 1.95 (s, 6H), 1.63 (s, 6H), 1.25 (t, J = 7.1Hz, 6H).

Synthesis of compound PLC-24

Compound PLC-24.1: 4'-(tert-butyl)-3-nitro-[1,1'-biphenyl]-4-ol 4-bromo-2-nitro-phenol (5.45 g, 25.0 mmol) and 4-(t-butyl)benzeneboronic acid (5.563 g, 31.25 mmol) were dissolved in dioxane (100 mL) at room temperature and stirred for 5 minutes. After forming a clear solution, Pd(PPh ₃ ) ₂ Cl ₂ (0.175 g, 0.25 mmol) and 4N aqueous K ₂ CO ₃ solution (25.0 ml, 50 mmol, 2 eq.) were added rapidly, and the mixture was heated in a Vac- After degassing three times by Fil nitrogen cycle, it was heated at 80° C. for 4 hours. After the reaction was cooled to room temperature, the pH was adjusted to 5-6 with 4N aqueous HCl, extracted with ethyl acetate (250 mL), and passed through a short pad of Celite. The pad was washed with EA (150ml x 2). The organic layers were combined, washed with brine (25 mL), dried over _anhydrous MgSO and concentrated under reduced pressure. The residue was dissolved in Hex:EA (95:5) (150 ml), the dark solid was filtered off by filtering through a short pad of Celite, and the filtrate was concentrated to give a yellow solid, which was triturated with hexane. This gave 3.8 yellow solids (56% yield). MS (APCI): Chemical formula: Calculated for C ₁₆ H ₁₇ NO ₃ (M-) = 271; Found: 271. ^1H NMR (400MHz, chloroform-d) δ 10.57 (s, 1H), 8.32 (d, J = 2.3Hz, 1H), 7.83 (dd, J = 8.7, 2.4Hz , 1H), 7.50 (d, J = 1.5Hz, 4H), 7.23 (d, J = 8.7Hz, 1H), 1.37 (s, 9H).

Compound PLC-24.2: 6-((4'-(tert-butyl)-3-nitro-[1,1'-biphenyl]-4-yl)oxy)-1H,3H-benzo[de]isochromene- 1,3-dione 4-bromonaphthalic anhydride (10 g, 36 mmol, 1.15 equivalents), 4'-(tert-butyl)-3-nitro-[1,1'-biphenyl]-4-ol (1574- 71) (8.5 g, 31.32 mmol, 1 eq.), NaOH (0.864 g, 21.6 mmol, 0.6 eq.) in anhydrous NMP (65 mL) and copper powder (1.371 g, 21.7 eq.) were mixed in anhydrous NMP (65 mL). 6 mmol, 0.6 eq) was added and the resulting mixture was degassed three times by Vac-Fil nitrogen cycle, then heated and stirred at 145° C. for 5 hours under N ₂ atmosphere and then at room temperature overnight. The RX mixture was worked up with aqueous HCl and after standing at room temperature for 12 hours, a brown solid precipitated, filtered and washed with hot MeOH (250 ml x 3) to give (10.8 g, 23.1 mmol) a light brown solid. A solid was obtained (73% yield, 86% purity). MS (APCI): Formula: Calculated for C ₂₈ H ₂₁ NO ₆ (M-) = 467; Found: 467.

Compound PLC-24.3: 6-((3-amino-4'-(tert-butyl)-[1,1'-biphenyl]-4-yl)oxy)-1H,3H-benzo[de]isochromene- 1,3-dione in a mixture of compound PLC-24.2 (4.885 g, 10.45 mmol, 1.0 eq.) in 2-MeTHF (70.0 mL) and HCl (4 M, 26.1 mL, 10 eq.). , SnCl ₂ .2H ₂ O (9.4 g, 41.75 mmol, 4.0 eq.) was added in one portion. The mixture was stirred at 90° C. for 1/2 hour. TLC (hexane/ethyl acetate = 7:3) and LCMS showed the reaction was complete. The white solid was filtered off and washed with EA/2-MeTHF (1:1) (100 mL x 2). The combined organic filtrates were washed with water, separated and concentrated under reduced pressure to give a sticky solid residue. The crude product was washed with 100 mL of hot water at 50 °C for 1/2 hour, filtered, and then dried under reduced pressure to give 1574-78 (4.5 g, 10.28 mmol) as a tan solid (98% yield). ) was obtained. MS (APCI): Chemical formula: Calculated value for C ₂₈ H ₂₃ NO ₄ (M-) = 437; Actual value: 437

Compound PLC-24.4: 9-(4-(tert-butyl)phenyl)-1H,3H-isochromeno[6,5,4-mna]xanthene-1,3-dione AcOH (28.5 mL) and H ₂ Compound PLC-24.3 (1.844 g, 4.215 mmol, 1.0 eq.) in O (9.0 mL) was dissolved in concentrated HCl (2.445 mL) in H ₂ O (9 mL) and NaNO ₂ (2.0 eq.). 9 g, 42.15 mmol, 10 equivalents) and stirred at 0° C. for 1 hour. The above solution was added to CuSO ₄ 5H ₂ O (4.35 g, 17.42 mmol, 4.1 eq.) in H ₂ O (175 ml), AcOH (11 ml) via addition funnel over 1/2 hour at 130 ml. Added at °C. After the addition was complete, the resultant was continued to stir for an additional 15 minutes at the same temperature of 130°C. The mixture was filtered and washed with _H2O (3 x 100 mL). →0.445g crude product was triturated with EtOH. →0.42g pure compound, 30% yield. MS (APCI): Formula: Calculated for C ₂₈ H ₂₀ O ₄ (M-) = 420; Found: 420.

Compound PLC-24.5: 9-(4-(tert-butyl)phenyl)-2-(3-hydroxypropyl)-1H-xanteno[2,1,9-def]isoquinoline-1,3(2H)- Dione Compound PLC-24.4 (0.420 g, 1.0 mmol, 1.0 equiv.) in anhydrous DMSO (4 mL) was dissolved in 3-amino-1-propanol (0.300 g, 4.0 mmol, 4.0 eq.) at room temperature. the resulting mixture was stirred at 130° C. for 45 minutes. After the reaction was completed, DMSO was removed by filtration. The solid was washed with water (50ml x 3) and dried in a vacuum oven to give 0.45g of a yellow solid (94% yield). MS (APCI): Formula: Calculated for C ₃₁ H ₂₇ NO ₄ (M-) = 477; Found: 477. ^1H NMR (400MHz, chloroform-d) δ 10.44 (s, 2H), 8.65 (d, J = 7.8Hz, 1H), 8.60 (d, J = 8.3Hz, 1H), 8.25 (d, J=2.0Hz, 1H), 8.03 (d, J=8.0Hz, 1H), 7.76 (dd, J=8.6, 2.1Hz, 1H), 7 .61 (d, J=8.3Hz, 2H), 7.54 (d, J=8.2Hz, 2H), 7.45 (d, J=8.6Hz, 1H), 7.32 (d, J=8.3Hz, 1H), 6.50 (s, 2H), 4.42 (t, J=6.9Hz, 2H), 4.17 (t, J=6.2Hz, 2H), 2. 54 (s, 6H), 2.28 (s, 2H), 1.40 (s, 9H).

Compound PLC-24.6: 2-(3-bromopropyl)-9-(4-(tert-butyl)phenyl)-1H-xanteno[2,1,9-def]isoquinoline-1,3(2H)- A mixture of dione compound 24.5 (0.453 g, 0.95 mmol) and 48% aqueous HBr (20 ml) was stirred and heated in a heat block at 130° C. for 8 hours. LCMS showed that the SM was completely consumed. The mixture was cooled to room temperature and left at room temperature for 16 hours. The yellow solid was filtered, washed several times with water, and dried in a vacuum oven to yield 0.275 g, 96% yield. The product was used in the next step without further purification. MS (APCI): Formula: Calculated for C ₃₁ H ₂₆ BrNO ₃ (M-) = 540; Found: 540. ^1H NMR (400MHz) δ 8.59 (d, J=7.8Hz, 1H), 8.53 (d, J=8.4Hz, 1H), 8.19 (s, 1H), 7.99 ( d, J = 8.0Hz, 1H), 7.72 (d, J = 8.7Hz, 1H), 7.55 (d, J = 8.0Hz, 2H), 7.45 (d, J = 8 .0Hz, 2H), 7.41 (d, J = 8.5Hz, 1H), 7.29 (d, J = 8.4Hz, 1H), 4.25 (s, 2H), 3.48 (d , J=6.1Hz, 2H), 3.16 (d, J=6.8Hz, 1H), 1.90 (s, 2H), 1.31 (s, 9H).

Compound PLC-24.7: 4-(3-(9-(4-(tert-butyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinoline-2(3H) -yl)propoxy)-2,6-dimethylbenzaldehyde 2,6-dichloro-4-hydroxybenzaldehyde (Combi Block, cas#60964-09-2), QF-6704 (batch 31758) in anhydrous DMF (1.0 ml) , 95% purity) (32 mg, 0.159 mmol, 1 eq.), K ₂ CO ₃ (32.5 mg, 0.23.5 mmol, 1.47 eq.), NaI (2.3 mg, catalytic amount) and 1643-011 A mixture of (96.74 mg, 0.179 mmol, 1.125 eq.) was mixed by sonication for 10 minutes before stirring at 85° C. for 4 hours under an argon atmosphere. LCMS showed only 10% conversion. The mixture was then heated and stirred to 65°C for 5 hours. After cooling to room temperature, the mixture was concentrated to dryness, the solid was washed with hot water (50 ml x 2), the yellow solid was collected by filtration, then sonicated with MeOH at room temperature, filtered and placed in a vacuum oven. The product was used in the next step without further purification to give 27.0 mg of 1643-015 (75% yield). MS (APCI): Formula: Calculated for C ₄₀ H ₃₅ NO ₅ (M-) = 609; Found: 609. ^1H NMR (400MHz, chloroform-d) δ 10.44 (s, 2H), 8.65 (d, J = 7.8Hz, 1H), 8.60 (d, J = 8.3Hz, 1H), 8.25 (d, J=2.0Hz, 1H), 8.03 (d, J=8.0Hz, 1H), 7.76 (dd, J=8.6, 2.1Hz, 1H), 7 .61 (d, J=8.3Hz, 2H), 7.54 (d, J=8.2Hz, 2H), 7.45 (d, J=8.6Hz, 1H), 7.32 (d, J=8.3Hz, 1H), 6.50 (s, 2H), 4.42 (t, J=6.9Hz, 2H), 4.17 (t, J=6.2Hz, 2H), 2. 54 (s, 6H), 2.28 (s, 2H), 1.40 (s, 9H).

Compound PLC-24: diethyl 10-(4-(3-(9-(4-(tert-butyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinoline-2( 3H)-yl)propoxy)-2,6-dimethylphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2', 1'-f][1,3,2]diazaborinine-2,8-dicarboxylate

Step 1: In a 50 ml vial (equipped with septum cap, magnetic stir bar), compound 1643-015 (68.28 mg, 0.112 mmol, 1 eq.) in anhydrous 1,2-dichloroethane (DCE) (2 ml), ethyl 2 ,4-dimethyl-1H-pyrrole-3-carboxylate (38.4 mg, 0.23 mmol, 2.05 eq.) was bubbled with argon, stirred at room temperature for 15 min, 4 mg of pTSA was added, and the RX After stirring for an additional 45 minutes at 86° C., LCMS showed complete conversion of starting material. The crude product was used in the next step in situ without further purification.

Step 2: The above mixture was cooled to room temperature and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) (79.45 mg, 0.35 mmol) was added in one portion. The resulting mixture was stirred at room temperature for 1/2 hour. TLC and LCMS showed complete conversion of starting material.

Step 3: The above mixture was cooled to 0°C and then stirred with triethylamine (0.125ml, 1.74mmol) for 15 minutes. BF ₃ etherate (0.71 mL, 2.76 mmol) was added dropwise. The resulting reaction mixture was stirred at 86° C. for 45 min under an argon atmosphere, cooled to 0° C., quenched with EtOH (2 ml) and the solvent was removed by rotary evaporation. The residue was chromatographed on a column of silica gel (80 g) eluting with DCM only (1 CV) then DCM/EtOAc (98:2), then washed with EtOH to give the pure title product (1643-017). was obtained as an orange-yellow solid (40 mg, 36% overall yield based on 1643-015 aldehyde SM). MS (APCI): Formula: Calculated for C ₅₈ H ₅₆ BF ₂ N ₃ O ₈ (M-) = 971; Found: 971. ¹ H NMR (400 MHz, chloroform-d) δ 8.65 (d, J = 7.8 Hz, 1H), 8.60 (d, J = 8.3 Hz, 1H), 8.24 (d, J = 2 .1Hz, 1H), 8.03 (d, J=8.0Hz, 1H), 7.75 (dd, J=8.6, 2.1Hz, 1H), 7.61 (d, J=8. 4Hz, 2H), 7.56-7.49 (m, 2H), 7.44 (d, J=8.6Hz, 1H), 7.32 (d, J=8.4Hz, 1H), 6. 64 (s, 2H), 4.45 (t, J = 6.9Hz, 2H), 4.28 (q, J = 7.1Hz, 4H), 4.15 (t, J = 6.3Hz, 2H ), 2.83 (s, 6H), 2.30 (t, J=6.7Hz, 2H), 2.02 (s, 6H), 1.71 (s, 6H), 1.56 (s, 6H), 1.40 (s, 9H), 1.33 (t, J=7.1Hz, 6H).

Synthesis of PLC-25

Compound PLC-25.1: 9-bromo-2-(4-hydroxybutyl)-1H-xanteno[2,1,9-def]isoquinoline-1,3(2H)-dione Attach a stirring bar to a 100 mL flask. Ta. In a flask were added compound PLC-3.3 (1.0 g, 2.7 mmol), 4-aminobutan-1-ol (485.3 mg, 5.4 mmol) and DMAP (23.1 mg, 0.0 mg) in DMF (20 ml). 19 mmol) was degassed at room temperature. The reaction mixture was heated to 165°C and the reaction was held at this temperature for 2.5 hours. TLC and LCMS showed the reaction was complete. The reaction was cooled to room temperature. _H2O (80ml) was added. The solid product was collected by vacuum filtration, washed with H ₂ O (100 ml), and further dried in a vacuum oven at 100 °C for 3 h, compound PLC as a brown solid for the next step without further purification. -25.1 was obtained. 908.0 mg, 77% yield. MS (APCI): Formula: Calculated for C ₂₂ H ₁₆ BrNO ₄ ([MH] ^- ) = 438; Found: 438. ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) 8.62 (d, J = 8.0 Hz, 1 H), 8.58 (d, J = 8.0 Hz, 1 H), 8.19 (d, J = 2 .4Hz, 1H), 7.93 (d, J=8.0Hz, 1H), 7.64 (dd, J=8.0Hz, J=2.4Hz, 2H), 7.32 (d, J= 8.0Hz, 1H), 7.28 (d, J = 8.0Hz, 1H), 4.20 (t, J = 7.2Hz, 2H), 3.83 (t, J = 6.0Hz, 2H) ), 1.82 (m, 2H), 1.69 (m, 2H).

Compound PLC-25.2: 2-(4-hydroxybutyl)-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)- Dione A stirring bar was attached to a 250 mL flask. In a flask, compound PLC- _25.1 (900.0 mg, 2.1 mmol), 4-(trifluoromethyl)phenylboronic acid (780.0 mg, 4.1 mmol), Pd(dppf) _Cl2 (107.5 mg, 0.15 mmol) and _K2CO3 ( _782.5 mg, 5.7 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 H ₂ O (150 ml) which was added to precipitate the product. The precipitate was collected by filtration. The solid was washed with H ₂ O (200 ml) and MeOH (20 ml) and further dried in a vacuum oven at 100 °C for 3 h to give compound 25.2 as a yellow solid for the next step without further purification. Obtained. 990.0 mg, 94% yield. MS ₍ APCI): Chemical formula: Calculated value for _C29H20F3NO4 ([M+H] ⁺ ) = 504; _{Found value} : 504. ^1H NMR (400MHz, _CDCl2CDCl2 ) 8.67 (d, J = 8.0Hz, _1H ), 8.61 (d, J = 8.0Hz, 1H), 8.27 (d, J = 2 .4Hz, 1H), 8.08 (d, J = 8.0Hz, 1H), 7.80 (m, 5H), 7.52 (d, J = 8.4Hz, 1H), 7.38 (d , J=8.4Hz, 1H), 4.22 (t, J=7.2Hz, 2H), 3.73 (t, J=6.0Hz, 2H), 1.84 (m, 4H).

Compound PLC-25.3: 4-(1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl) Butyl 4-methylbenzenesulfonate A 100 mL flask was equipped with a stirring bar. Compound PLC-25.2 (200.0 mg, 0.40 mmol) and DCE (20 ml) were added to the flask. The solution was degassed at room temperature and p-toluenesulfonic anhydride (519.0 mg, 1.6 mmol) and TEA (221.0 μL, 1.6 mmol) were added. The solution was then heated to 90°C and held at this temperature for 4 hours. The reaction was monitored using TLC and LCMS. Furthermore, DCE (20 mL) and p-toluenesulfonic anhydride (519.0 mg, 1.6 mmol) were added. The reaction was cooled to room temperature. H ₂ O (100 ml) and TEA (221.0 μL, 1.6 mmol) were added. The reaction was held at 90°C overnight. The mixture was quenched with H ₂ O (150 ml) and then extracted with DCM (150 ml x 3). The combined organic phases were dried over anhydrous Na ₂ SO ₄ and concentrated under a vacuum rotary evaporator to yield compound PLC-25.3 as a yellow solid, which was used in the next step without further purification. MS (APCI): Chemical formula: Calculated value for C ₃₆ H ₂₆ F ₃ NO ₆ S ([MH] ^- ) = 657; Observed value: 657. ^1H NMR (400MHz, _CDCl3 ) 8.55 (d, J = 8.0Hz, 1H), 8.51 (d, J = 8.0Hz, 1H), 8.16 (d, J = 2.0Hz , 1H), 7.92 (d, J = 8.0Hz, 1H), 7.76 (m, 7H), 7.41 (d, J = 8.4Hz, 1H), 7.32 (d, J = 8.0Hz, 2H), 7.24 (d, J = 8.0Hz, 1H), 4.10 (m, 4H), 2.42 (s, 3H), 1.76 (m, 4H).

Compound PLC-25.4: 4-(4-(1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinoline-2(3H) -yl)butoxy)-2,6-dimethylbenzaldehyde In a 25 ml vial, compound PLC-25.3 (131.5 mg, 0.20 mmol) and 4-hydroxy-2,6-methylbenzaldehyde ( 33.0 mg, 0.22 mmol). The solution was degassed at room temperature and K ₂ CO ₃ (41.4 mg, 0.30 mmol) was added. The reaction was further degassed at room temperature. Thereafter, it was heated to 65° C. and continued stirring at this temperature overnight. TLC (50% EtOAc in hexanes) showed completion of the reaction. The reaction mixture was purified by silica gel flash chromatography using EtOAc in hexane (0% → 40% → 60%) as eluent to give pure compound PLC-25.4 as a solid (30.0 mg, 24% yield (over two steps). MS (APCI): Chemical formula: Calculated value for C ₃₈ H ₂₈ F ₃ NO ₅ ([MH] ^- ) = 635; Found value: 635. ^1H NMR (400MHz, _CDCl3 ) δ 10.43 (s, 1H), 8.64 (d, J = 8.0Hz, 1H), 8.60 (d, J = 8.0Hz, 1H), 8 .23 (d, J=2.4Hz, 1H), 8.02 (d, J=8.0Hz, 1H), 7.77 (s, 4H), 7.74 (dd, J=8.0Hz, 2.0Hz, 1H), 7.47 (d, J = 8.0Hz, 1H), 7.31 (d, J = 8.0Hz, 1H), 6.56 (s, 2H), 4.28 ( t, J = 6.8 Hz, 2H), 4.07 (t, J = 6.0Hz, 2H), 1.94 (m, 6H), 1.58 (m, 4H).

Compound PLC-25: diethyl 10-(4-(4-(1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinoline-2( 3H)-butoxy)-2,6-dimethylphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1' -f][1,3,2]diazaborinine-2,8-dicarboxylate A 100 mL two-necked round bottom flask was equipped with an air condenser and a stir bar.The flask was charged with compound 25.4 (67.0 mg, 0 .1 mmol) and ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (37.0 mg, 0.2 mmol) were added, followed by anhydrous dichloroethane (7 ml). The reaction mixture was sparged with Ar for 30 min. followed by the addition of p-TsOH.H ₂ O (0.67 mg, 0.006 mmol). The reaction solution was heated to 85° C. and kept at this temperature overnight. The reaction was then cooled to room temperature. , DDQ (13.7 mg, 0.06 mmol) was added. The reaction was kept at room temperature for 30 min. BF ₃ .OEt ₂ (0.16 mL, 1.3 mmol) and Et ₃ N (0.12 mL, 0.9 mmol) was added at room temperature. The reaction mixture was heated to 60° C. and held at this temperature for 1 hour. At room temperature, additional BF ₃ .OEt ₂ (0.16 mL, 1.3 mmol) and Et ₃ N ( 0.12 mL, 0.9 mmol) was added. The reaction mixture was heated to 60 °C and kept at this temperature for 3 hours. The reaction mixture was loaded on silica gel and DCM (0% → 10% → 14% ) to give pure compound PLC-25 as an orange solid (12.0 mg, 11% yield). MS (APCI): Formula: C ₅₆ H ₄₉ BF Calculated value for ₅ N ₃ O ₈ ([MH] ^- ) = 997; Actual value: 997. ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) 8.68 (d, J = 8.0 Hz, 1 H) , 8.62 (d, J = 8.0 Hz, 1H), 8.28 (d, J = 2.0 Hz, 1H), 8.09 (d, J = 8.0 Hz, 1H), 7.79 ( m, 5H), 7.52 (d, J = 8.0Hz, 1H), 7.39 (d, J = 8.0Hz, 1H), 6.75 (s, 2H), 4.27 (m, 6H), 4.07 (m, 2H), 2.82 (s, 6H), 2.07 (s, 6H), 1.97 (m, 4H), 1.72 (s, 6H), 1. 33 (t, J=7.2Hz, 6H).

Synthesis of compound PLC-26

Compound PLC-26.2: 4-(2-(2-(2-(1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def] Isoquinolin-2(3H)-yl)ethoxy)ethoxy)ethoxy)-2,6-dimethylbenzaldehyde In a 25 ml vial were added compounds PLC-26.1 (186.6 mg, 0.26 mmol) and 4 in DMF (5 mL). -Hydroxy-2,6-methylbenzaldehyde (43.0 mg, 0.29 mmol) was added. The solution was degassed at room temperature and K ₂ CO ₃ (53.8 mg, 0.39 mmol) was added. The reaction was further degassed at room temperature. It was then warmed to 65° C. and continued stirring at this temperature overnight. TLC (50% EtOAc in hexanes) showed completion of the reaction. The reaction mixture was purified by silica gel flash chromatography using EtOAc in hexane (0%→40%→60%) as eluent to yield pure compound PLC-26.2 as a yellow solid (70.0 mg, 39% yield (over two steps). MS (APCI): Chemical formula: Calculated value for C ₄₀ H ₃₂ F ₃ NO ₇ ([MH] ^- ) = 695; Found value: 695. ^1H NMR (400MHz, _CDCl2CDCl2 ) δ 10.30 (s, _1H ), 8.58 (d, J=8.0Hz, 1H), 8.54 (d, J=8.0Hz, 1H) , 8.16 (d, J=2.0Hz, 1H), 7.95 (d, J=8.0Hz, 1H), 7.79 (s, 4H), 7.75 (dd, J=8. 0Hz, 2.0Hz, 1H), 7.44 (d, J=8.0Hz, 1H), 7.28 (d, J=8.0Hz, 1H), 6.40 (s, 2H), 4. 43 (t, J = 6.0Hz, 2H), 3.90 (t, J = 4.4Hz, 2H), 3.84 (t, J = 6.0Hz, 2H), 3.72 (m, 6H) ), 2.48 (s, 6H).

Compound PLC-26: diethyl 10-(4-(2-(2-(2-(1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9- def]isoquinolin-2(3H)-yl)ethoxy)ethoxy)ethoxy)-2,6-dimethylphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo [1,2-c:2',1'-f][1,3,2]Diazaborinine-2,8-dicarboxylate A 100 mL two-neck round bottom flask was equipped with an air condenser and a stir bar. To the flask were added compound PLC-26.2 (70.0 mg, 0.1 mmol) and ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (35.3 mg, 0.2 mmol), followed by anhydrous dichloroethane. (5 ml) was added. The reaction mixture was sparged with Ar for 30 min, then p-TsOH.H ₂ O (3.7 mg, 0.03 mmol) was added. The reaction solution was heated to 65°C and kept at this temperature overnight. The reaction was then cooled to room temperature and DDQ (12.4 mg, 0.06 mmol) was added. The reaction was held at room temperature for 30 minutes. Then BF ₃ .OEt ₂ (0.15 mL, 1.2 mmol) and Et ₃ N (0.11 mL, 0.8 mmol) were added at room temperature. The reaction mixture was heated to 60°C and held at this temperature for 1 hour. The reaction mixture was loaded onto silica gel and purified by flash chromatography using EtOAc in DCM (0%→10%) as eluent to give pure compound PLC-26 as an orange solid (28.0 mg, 26% yield). (%). MS (APCI): Chemical formula: C ₅₈ H ₅₃ BF ₅ N ₃ O Calculated value for ₁₀ ([MH] ^- ) = 1057; Found value: 1057. ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) 8.67 (d, J = 8.0 Hz, 1 H), 8.62 (d, J = 8.0 Hz, 1 H), 8.26 (d, J = 2 .4Hz, 1H), 8.07 (d, J = 8.0Hz, 1H), 7.79 (bs, 4H), 7.77 (dd, J = 8.0Hz, 2.0Hz, 1H), 7 .51 (d, J=8.0Hz, 1H), 7.37 (d, J=8.0Hz, 1H), 6.73 (s, 2H), 4.45 (t, J=6.0Hz, 2H), 4.27 (q, J = 7.2Hz, 4H), 4.09 (m, 2H), 3.84 (m, 4H), 3.74 (m, 4H), 2.82 (s , 6H), 2.07 (s, 6H), 1.72 (s, 6H), 1.33 (t, J=7.2Hz, 6H).

Synthesis of compound PLC-27

Compound PLC-27.1: 9-bromo-2-(3-hydroxypropyl)-1H-xanteno[2,1,9-def]isoquinoline-1,3(2H)-dione Attach a stirring bar to a 100 mL flask. Ta. In a flask, compound PLC-3.3 (500.0 mg, 1.4 mmol), 3-aminopropan-1-ol (204.6 mg, 2.7 mmol) and DMAP (11.6 mg, 0 .1 mmol) was degassed at room temperature. The reaction mixture was heated to 165°C and the reaction was held at this temperature for 2 hours. TLC and LCMS showed the reaction was complete. The reaction was cooled to room temperature. _H2O (85ml) was added to precipitate the product. The precipitate was collected by filtration. The solid was washed with H ₂ O (150 ml) and further dried in a vacuum oven at 100° C. for 3 hours to give compound PLC-27.1 as a yellow solid for the next step without further purification. 455.0 mg, 79% yield. MS (APCI): Chemical formula: Calculated value for C ₂₁ H ₁₄ BrNO ₄ ([MH] ^- ) = 423; Found value: 423. ^1H NMR (400MHz, _CDCl2CDCl2 ) 8.62 (d, J = 8.0Hz, _1H ), 8.59 (d, J = 8.0Hz, 1H), 8.18 (s, 1H), 7.91 (d, J=8.0Hz, 1H), 7.64 (dd, J=8.0Hz, J=2.0Hz, 1H), 7.33 (d, J=8.0Hz, 1H) , 7.28 (d, J=8.0Hz, 1H), 4.32 (t, J=6.0Hz, 2H), 3.56 (m, 2H), 3.16 (bs, 1H), 1 .98 (m, 2H).

Compound PLC-27.2: 2-(3-hydroxypropyl)-9-(perfluorophenyl)-1H-xanteno[2,1,9-def]isoquinoline-1,3(2H)-dione in a 100 mL flask. A stirrer was attached. In a flask, compound PLC-27.1 (400.0 mg, 0.9 mmol), (perfluorophenyl)boronic acid (240.0 mg, 1.1 mmol), Pd ₂ (dba) ₃ (43 .0 mg, 0.05 mmol), CsF (285.6 mg, 1.9 mmol), Ag ₂ O (259.4 mg, 1.1 mmol) and (t-Bu) ₃ P (1.9 ml, 1.9 mmol) at room temperature. I degassed it. 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 purified by silica gel flash chromatography using EtOAc in hexane (5%→10%→50%→70%) as eluent to give pure compound PLC-27.2 as a yellow solid (136 .0 mg, 28% yield). MS (APCI): Chemical formula: Calculated value for C ₂₇ H ₁₄ F ₅ NO ₄ ([MH] ^- ) = 511; Found value: 511. ^1H NMR (400MHz, _CDCl2CDCl2 ) 8.57 (d, J = 8.0Hz, _1H ), 8.55 (d, J = 8.0Hz, 1H), 8.07 (s, 1H), 7.92 (d, J=8.0Hz, 1H), 7.53 (d, J=8.0Hz, 1H), 7.46 (d, J=8.0Hz, 1H), 7.32 (d , J=8.0Hz, 1H), 4.25 (t, J=6.0Hz, 2H), 3.48 (m, 2H), 3.07 (t, J=6.8Hz, 1H), 1 .90 (m, 2H).

Compound PLC-27.3: 2-(3-bromopropyl)-9-(perfluorophenyl)-1H-xanteno[2,1,9-def]isoquinoline-1,3(2H)-dione in a 100 mL flask. A stirrer was attached. Compound PLC-27.2 (136.0 mg, 0.3 mmol), CBr (176.3 mg, 0.5 mmol), _PPh (140.2 mg, 0.5 mmol) and DCE (12 ml ₎ were added to the flask. . The solution was degassed at room temperature. The reaction was held at this temperature for 30 minutes. The reaction was monitored using TLC and LCMS. After completion, the reaction was purified by silica gel flash chromatography using EtOAc in hexane (5%→10%→50%→70%) as eluent to give pure compound PLC-27.3 as a yellow solid (116 .0 mg, 76% yield). MS ₍ APCI): Formula: Calculated for _{C27H13BrF5NO3} ([M+H] ⁺ ) = 573; _{Found :} 573. ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) 8.64 (d, J = 8.0 Hz, 1 H), 8.61 (d, J = 8.0 Hz, 1 H), 8.15 (d, J = 1 .6Hz, 1H), 7.99 (d, J = 8.0Hz, 1H), 7.61 (m, 1H), 7.54 (d, J = 8.0Hz, 1H), 7.39 (d , J=8.0Hz, 1H), 4.32 (t, J=6.8Hz, 2H), 3.54 (t, J=6.8Hz, 2H), 2.34 (quintet, J=6. 8Hz, 2H).

Compound PLC-27.4: 4-(3-(1,3-dioxo-9-(perfluorophenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)propoxy) -2,6-dimethylbenzaldehyde In a 25 ml vial, compound PLC-27.3 (50.0 mg, 0.09 mmol), 4-hydroxy-2,6-dimethylbenzaldehyde (15.7 mg, 0.1 mmol), K _{2 CO3} (24.0 mg, 0.2 mmol) and DMF (2 ml) were added. The mixture was sonicated for 2 minutes at room temperature. It was then heated to 75°C and continued stirring at this temperature for 4 hours. TLC (50% EtOAc in hexanes) showed completion of the reaction. The reaction mixture was purified by silica gel flash chromatography using EtOAc in DCM (0%→40%) as eluent to give pure compound PLC-27.4 as a yellow solid (29.0 mg, 48% yield). ) was obtained. MS (APCI): Chemical formula: Calculated value for C ₃₆ H ₂₂ F ₅ NO ₅ ([MH] ^- ) = 643; Found value: 643. ^1H NMR (400MHz, _CDCl2CDCl2 ) δ 10.43 (s, _1H ), 8.63 (d, J=8.0Hz, 1H), 8.59 (d, J=8.0Hz, 1H) , 8.15 (bs, 1H), 7.99 (d, J=8.0Hz, 1H), 7.61 (d, J=8.0Hz, 1H), 7.54 (d, J=8. 0Hz, 1H), 7.38 (d, J = 8.0Hz, 1H), 6.55 (s, 2H), 4.39 (t, J = 6.8Hz, 2H), 4.17 (t, J=6.8Hz, 2H), 2.56 (s, 6H), 2.26 (quintet, J=6.8Hz, 2H).

Compound PLC-27: Diethyl 10-(4-(3-(1,3-dioxo-9-(perfluorophenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl) propoxy)-2,6-dimethylphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f] [1,3,2]Diazaborinine-2,8-dicarboxylate A 50 mL two-neck round bottom flask was equipped with an air condenser and a stir bar. Compound 27.4 (60.0 mg, 0.1 mmol) and ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (32.7.0 mg, 0.2 mmol) were added to the flask, followed by anhydrous dichloroethane. (5 ml) was added. The reaction mixture was sparged with Ar for 30 min, then p-TsOH.H ₂ O (0.7 mg, 0.006 mmol) was added. The reaction solution was heated to 65°C and kept at this temperature overnight. The reaction was then cooled to room temperature and DDQ (11.2 mg, 0.05 mmol) was added. The reaction was held at room temperature for 30 minutes. Then BF ₃ .OEt ₂ (0.13 mL, 1.1 mmol) and Et ₃ N (0.10 mL, 0.7 mmol) were added at room temperature. The reaction mixture was heated to 60°C and held at this temperature for 1 hour. The reaction mixture was loaded on silica gel and purified by flash chromatography using EtOAc in DCM (0%→10%) as eluent to give pure compound PLC-27 as an orange solid (77.0 mg, 85% yield). (%). MS (APCI): Chemical formula: Calculated value for C ₅₄ H ₄₃ BF ₇ N ₃ O ₈ ([MH] ^- ) = 1005; Observed value: 1005. ^1H NMR (400MHz, _CDCl2CDCl2 ) 8.64 (d, J = 8.0Hz, _1H ), 8.61 (d, J = 8.0Hz, 1H), 8.15 (bs, 1H), 8.00 (d, J=8.0Hz, 1H), 7.61 (d, J=8.0Hz, 1H), 7.54 (d, J=8.0Hz, 1H), 7.39 (d , J=8.0Hz, 1H), 6.67 (s, 2H), 4.41 (t, J=6.8Hz, 2H), 4.27 (q, J=7.2Hz, 4H), 4 .171 (t, J=6.8Hz, 2H), 2.82 (s, 6H), 2.28 (quintet, J=6.8Hz, 2H), 2.05 (s, 6H), 1.72 (s, 6H), 1.34 (t, J=7.2Hz, 6H).

Synthesis of compound PLC-29

Compound PLC-29.1: 6-(2-nitro-4-(trifluoromethyl)phenoxy)-1H,3H-benzo[de]isochromene-1,3-dione A 1 L 2N round bottom flask was heated in an aluminum heat exchanger. It was placed in a block and a stirring bar 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 2-nitro-4-(trifluoromethyl)phenol (60.0 mmol, 8.0 mmol) were placed in a flask. 44 mL) 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 heat block was set at 170° C. and the flask was stirred under an argon atmosphere. 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 was further diluted with water (325 mL) to obtain a sticky precipitate. The reaction mixture was decanted from the sticky precipitate and washed with water. The crude product was evaporated to dryness under vacuum, then dissolved in DCM and evaporated onto about 65 g of flash silica gel. Purified by silica gel flash chromatography (330 g, solids, equilibrated 100% hexanes, elution 100% (2 CV) → 100% DCM (20 CV)). Fractions containing the product were collected and evaporated to dryness in vacuo. 1.558 g (10% yield) of a light brown solid was obtained (approximately 80% pure). Used in next step without further purification. MS _{(APCI): Formula: Calculated for C19H8F3NO6 (} M+H) = 404; Found _{: 404} .

Compound PLC-29.2: (6-(2-amino-4-(trifluoromethyl)phenoxy)-1H,3H-benzo[de]isochromene-1,3-dione)
Compound PLC-29.2 was prepared similarly to the method described above, with compound PLC-29.1 (3.47 mmol, 1.400 g), SnCl ₂ .2H ₂ O (13.88 mmol, 3131 mg) in 2MeTHF (30 mL). , 4N HCl (34.7 mmol, 8.7 mL). After normal work-up, the product was pure enough to be used in the next step. 877 mg (68% yield) was obtained. MS ₍ APCI): Formula: Calculated for _C19H10F3NO4 (M+H) = ₃₇₄ ; Found _: 374. ¹ H NMR (400 MHz, tetrachloroethane-d ₂ ) δ 8.85 (dd, J=8.4, 1.2 Hz, 1H), 8.69 (dd, J=7.3, 1.2 Hz, 1H) , 8.49 (d, J = 8.3 Hz, 1H), 7.91 (dd, J = 8.4, 7.3 Hz, 1H), 7.20 (d, J = 2.0 Hz, 1H), 7.17-7.07 (m, 2H), 6.98 (d, J=8.3Hz, 1H), 4.07 (s, 2H).

Compound PLC-29.3: (9-(trifluoromethyl)-1H,3H-isochromeno[6,5,4-mna]xanthene-1,3-dione)
Compound PLC-29.3 was mixed with compound PLC-29.2 (2.344 mmol, 875 mg), NaNO ₂ (17.58 mmol, 1.213 g), concentrated HCl (11.72 mmol, 12.1 N, 0.969 mL), and Synthesized from CuSO ₄ .5H ₂ O (16.06 mmol, 4.009 g). The crude product was evaporated in vacuo onto about 30 g of flash silica gel. Purified by silica gel flash chromatography (220 g, solids, no equilibration, elution 100% hexane (2 CV) → 100% DCM (20 CV) → isocratic DCM + 0.5% EtOAc modifier). Fractions containing product were evaporated to dryness in vacuo. 509 mg (61% yield) of a yellow solid was obtained. MS ₍ APCI): Formula: Calculated for _C19H7F3O4 (M+H) ₌ 357; _Found : 357. ¹ H NMR (400 MHz, tetrachloroethane-d ₂ ) δ 8.64 (d, J = 7.9 Hz, 1H), 8.60 (d, J = 8.3 Hz, 1H), 8.34-8.28 (m, 1H), 8.04 (d, J=7.9Hz, 1H), 7.82 (dd, J=8.9, 2.0Hz, 1H), 7.52 (d, J=8. 6Hz, 1H), 7.40 (d, J=8.3Hz, 1H).

Compound PLC-29.4: (2-(4-(1,3-dioxo-9-(trifluoromethyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl ) acetic acid)
Compound PLC-29.4 was prepared in a manner similar to the method described above, including compound PLC-29.3 (0.702 mmol, 250 mg), 2-(4-aminophenyl)acetic acid (1.754 g, 265 mg) in DMF (10 mL). ), and DMAP (0.0521 mmol, 6.3 mg). After work-up and trituration, the compound was dried in a vacuum oven at about 140°C. 366 mg (107% yield) was obtained. MS ₍ APCI): Formula: Calculated for _C19H7F3O4 (M+ _H ) ₌ 490; Found: 490. ^1H NMR (400MHz, DMSO- _d6 ) δ 8.65 (d, J=2.2Hz, 1H), 8.45-8.37 (m, 4H), 7.90 (dd, J=8. 8, 2.2Hz, 1H), 7.62 to 7.56 (m, 1H), 7.45 to 7.38 (m, 2H), 7.31 to 7.24 (m, 2H), 3. 68 (s, 2H).

Compound PLC-29: diethyl 10-(4-(2-(4-(1,3-dioxo-9-(trifluoromethyl)-1H-xantheno[2,1,9-def]isoquinoline-2(3H) -yl)phenyl)acetoxy)-2,6-dimethylphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2', 1'-f][1,3,2]diazaborinine-2,8-dicarboxylate Compound PLC-29 was added to compound PLC-1.1 (0.050 mmol, 25.6 mg), compound PLC-1.1 (0.050 mmol, 25.6 mg), and compound It was synthesized from PLC-29.4 (0.075 mmol, 37 mg), DMAP・pTsOH salt (0.100 mmol, 29.4 mg) and EDC・HCl (0.150 mmol, 28.8 mg). The crude product was diluted with hexane and loaded onto approximately 30 g of flash silica gel in a solids loader. Silica gel flash chromatography (80 g, solids, no equilibration, elution 100% hexane/0.5% EtOAc modifier (2 CV) → 100% DCM/0.5% EtOAc modifier (10 CV) → 100% DCM /1% EtOAc modifier (20CV) → 100% DCM/2% EtOAc modifier (20CV) → 100% DCM/4% EtOAc modifier (20CV)). Fractions containing product were evaporated to dryness in vacuo. 46 mg (94% yield) of an orange solid was obtained. MS (APCI): Chemical formula: C ₅₄ H ₄₃ BF ₅ N ₃ O Calculated value (M-) for ₉ = 983; Found value: 983. ¹ H NMR (400 MHz, tetrachloroethane-d ₂ ) δ 8.68 (d, J = 7.8 Hz, 1H), 8.64 (d, J = 8.3 Hz, 1H), 8.34 (d, J = 2.1Hz, 1H), 8.07 (d, J = 8.0Hz, 1H), 7.81 (dd, J = 8.9, 2.0Hz, 1H), 7.67 to 7.62 ( m, 2H), 7.52 (d, J = 8.6Hz, 1H), 7.41 (d, J = 8.3Hz, 1H), 7.40 to 7.35 (m, 2H), 7. 05 (s, 2H), 4.28 (q, J = 7.1Hz, 4H), 4.01 (s, 2H), 2.84 (s, 6H), 2.16 (s, 6H), 1 .73 (s, 6H), 1.34 (t, J=7.1Hz, 6H).

Synthesis of compound PLC-32

Compound PLC-32.1: 9-bromo-2-(6-hydroxyhexyl)-1H-xanteno[2,1,9-def]isoquinoline-1,3(2H)-dione Compound PLC-32.1, Similar to the above method, compound PLC-3.3 (6.534 mmol, 2.401 g), 6-aminohexan-1-ol (13.08 mmol, 1533 mg) and DMAP (1.962 mmol, 240 mg) were synthesized. . The crude product was filtered off, washed with water, and the wet precipitate was used in the next step without further purification. MS (APCI): Formula: Calculated for _C24H20BrNO4 (M+H) = 466; Found _{: 466} .

Compound PLC-32.2 2-(6-hydroxyhexyl)-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione Compound PLC-32.2 was prepared as compound PLC-32.1 (100% yield) in THF (120 mL)/DMF (24 mL)/H ₂ O (12 mL) at 80° C., similar to the method described above. _{Assuming that} ) Synthesized from Cl ₂ (0.4574 mmol, 335 mg). After adding water and filtration, the resulting precipitate was washed with water and then with methanol. The product was dried by suction and then in vacuo. 1.191 g (34% yield based on compound PLC-3.3, 2 steps) was obtained. MS (APCI): Formula: Calculated for _C31H24F3NO4 ( _M + _H ) = 532; Found _: 532.

Compound PLC-32.3: 2-(6-bromohexyl)-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)- A stirrer was placed in 250 mL of 2N RBF, and a gas adapter/finned condenser and flow controller were attached. Compound PLC-32.2 (2.239 mmol, 1.190 g) was added to the flask followed by 48% HBr/H ₂ O (30 mL). The heat block was set at 130° C. and the reaction mixture was stirred at this temperature for 3 hours. Another portion of 48% HBr/H ₂ O (30 mL) was added and the reaction mixture was stirred at 130° C. overnight. The reaction mixture was cooled to room temperature, diluted with water (approximately 100 mL), then the precipitate was filtered off and washed with water and then methanol. The product was loaded onto approximately 25g of silica gel in a loader. Purified by silica gel flash chromatography (120 g, solids, equilibrated 0% EtOAc/DCM, 0% (2 CV) → 10% EtOAc/DCM (20 CV)). Fractions containing the product were collected and evaporated to dryness in vacuo. A material of approximately 80% purity was obtained. A yellow solid, 1.073 g (80% yield) was obtained. MS (APCI): Formula: Calculated _{for C31H23BrF3NO3} ( _M +H) = 594; _Found : 594. ^1H NMR (400MHz, TCE) δ 8.63 (d, J = 7.9Hz, 1H), 8.58 (d, J = 8.3Hz, 1H), 8.23 (d, J = 2.1Hz , 1H), 8.03 (d, J = 8.0Hz, 1H), 7.84 to 7.73 (m, 5H), 7.49 (d, J = 8.6Hz, 1H), 7.34 (d, J=8.3Hz, 1H), 4.19-4.09 (m, 2H), 3.44 (td, J=6.8, 1.9Hz, 2H), 1.90 (p, J=6.9Hz, 2H), 1.75 (p, J=7.8Hz, 2H), 1.57-1.38 (m, 4H).

Compound PLC-32.4 4-((6-(1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinoline-2(3H) -yl)hexyl)oxy)-2,6-dimethylbenzaldehyde Compound PLC-32.4 was dissolved in dry DMF (10 mL) with compound PCL-32.3 (0.200 mmol, 119 mg), 4-hydroxy-2, Synthesized from 6-dimethylbenzaldehyde (0.300 mmol, 45 mg) and K ₂ CO ₃ (0.260 mmol, 36 mg). The reaction mixture was sonicated for 15 minutes and then stirred in a heat block at 65° C. for 7 hours. Heating was removed and water was added to the hot reaction mixture (approximately 100 mL), which produced no precipitate. The aqueous layer was saturated with NaCl and then extracted with THF (1 x 200 mL, 2 x 50 mL). The combined organic layers were dried with _MgSO4 , filtered and evaporated to dryness in vacuo. The crude product was dissolved in DCM and loaded onto approximately 5 g of silica gel in a loader. Silica gel flash chromatography (80 g, solids, equilibrated 70% DCM/hexane, elution 70% (2 CV) → 100% DCM/hexane (5 CV) → isocratic 100% DCM/hexane (5 CV) → 0% EtOAc/ Purified by DCM (0 CV) → isocratic 0% EtOAc/DCM (5 CV) → 10% EtOAc/DCM (20 CV). Fractions containing product were evaporated to dryness in vacuo. A yellow solid, 95 mg (71% yield) was obtained. MS (APCI): Formula: Calculated for _C40H32F3NO5 ( _M +H) = 664; Found _{: 664} . ^1H NMR (400MHz, TCE) δ 10.42 (s, 1H), 8.64 (d, J=7.9Hz, 1H), 8.59 (d, J=8.3Hz, 1H), 8. 25 (d, J = 2.2Hz, 1H), 8.05 (d, J = 8.0Hz, 1H), 7.84 to 7.74 (m, 5H), 7.51 (d, J = 8 .5Hz, 1H), 7.36 (d, J = 8.3Hz, 1H), 6.60 (s, 2H), 4.20 to 4.15 (m, 2H), 4.01 (t, J =6.4Hz, 2H), 2.59 (s, 6H), 1.89 to 1.70 (m, 4H), 1.60 to 1.43 (m, 4H).

Compound PLC-32: diethyl 10-(4-((6-(1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinoline-2 (3H)-yl)hexyl)oxy)-2,6-dimethylphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c: 2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylate Compound PLC-32 was treated in the same manner as compound 32, compound PLC-32.4 (0.1401 mmol, 93 mg), Ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (0.0.2943 mmol, 49 mg) in dry DCE (20 mL) followed by pTsOH.H ₂ O (0.0140 mmol, 2.7 mg) then Synthesized from DDQ (0.0.2382 mmol, 54 mg), 2×Et ₃ N (1.121 mmol, 0.156 mL) and BF ₃ .OEt ₂ (1.682 mmol, 0.208 mL). The crude reaction mixture was diluted with hexane (approximately 25%) and then loaded onto approximately 5 g of silica gel in a loader. Silica gel flash chromatography (80 g, solids, equilibrated 70% DCM/hexane, elution 70% (2 CV) → 100% DCM/hexane (5 CV) → isocratic 100% DCM/hexane (5 CV) → 0% EtOAc/ Purified by DCM (0 CV) → isocratic 0% EtOAc/DCM (5 CV) → 10% EtOAc/DCM (20 CV). Fractions containing product were evaporated to dryness in vacuo. 26 mg (18% yield) of an orange solid was obtained. MS ( _APCI ): Formula: Calculated for _{C58H53BF5N3O8} ( _M +H) ₌ 1026; _Found : 1026. ¹ H NMR (400 MHz, TCE) δ 8.56 (d, J = 7.8 Hz, 1H), 8.51 (d, J = 8.4 Hz, 1H), 8.16 (d, J = 2.3 Hz) , 1H), 7.97 (d, J = 8.0Hz, 1H), 7.77 to 7.65 (m, 5H), 7.42 (d, J = 8.6Hz, 1H), 7.27 (d, J=8.3Hz, 1H), 6.66 (s, 2H), 4.18 (q, J=7.1Hz, 4H), 4.10 (dd, J=8.8, 6. 6Hz, 2H), 3.92 (t, J=6.5Hz, 2H), 2.74 (s, 6H), 1.99 (s, 6H), 1.82 to 1.67 (m, 4H) , 1.65 (s, 6H), 1.52-1.38 (m, 4H), 1.24 (t, J=7.1Hz, 6H).

Synthesis of compound PLC-33

Compound PLC-33.1: 2-(2-(2-methoxyethoxy)ethoxy)ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate)
A stirrer was placed in 100 mL of 2N RBF, and a gas adapter/finned condenser and flow controller were attached. The system was flushed with argon. NaH (60% mineral oil, 45.00 mmol, 1800 mg) was added to the flask. The mixture was stirred at room temperature and 2-(2-(2-methoxyethoxy)ethoxy)ethan-1-ol (90.00 mmol, 14.4 mL) was carefully added. When hydrogen gas evolution stopped, ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (30.00 mmol, 5.016 g) was added. The system was closed and stirred under an argon atmosphere. The heat block was set at 130° C. and the reaction mixture was stirred at this temperature for 30 minutes. LCMS shows about 45:55 product:starting material. The reaction was continued for several more hours at 130°C, with little change in the ratio. A vent was installed at the top of the findenser and opened to allow the ethanol to escape. After about 5 hours of heating, less than 5% of the starting ester remained. The reaction mixture was cooled to room temperature and water was added. Since no precipitate formed, the reaction mixture was treated with NaCl to break the emulsion and then extracted with ethyl acetate (3 x 100 mL). The combined organic layers were washed with brine (50 mL), dried over _MgSO4 , filtered and evaporated to dryness in vacuo. A dark brown oil was obtained. The vial was heated at 140° C. under a flow of argon to remove excess alcohol. 6.839 g (80% yield) was obtained. MS (APCI): Formula: Calculated for _C14H23NO5 ( _M +H) ₌ 286; Found: 286. ^1H NMR (400MHz, TCE) δ 8.07 (s, 1H), 6.39 (dd, J=2.3, 1.2Hz, 1H), 4.38-4.31 (m, 2H), 3.81-3.74 (m, 2H), 3.69-3.65 (m, 2H), 3.65-3.58 (m, 4H), 3.56-3.50 (m, 2H) ), 3.35 (s, 3H), 2.48 (s, 3H), 2.23 (d, J = 1.1Hz, 3H).

Compound PLC-33.2: bis(2-(2-(2-methoxyethoxy)ethoxy)ethyl)5,5-difluoro-10-(4-hydroxy-2,6-dimethylphenyl)-1,3,7 ,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylate Compound PLC-33.2 was mixed with compound PLC-33.1 (3.588 mmol, 1024 mg), 4-hydroxy-2,6-dimethylbenzaldehyde (1.750 mmol, 263 mg) and pTsOH in dry DCE (50 mL) in the same manner as above. _H2O (0.175 mmol, 33 mg) followed by DDQ (2.975 _mmol , 675 mg) and _2xEt3N (14.00 mmol, 1.95 mL) and _BF3.OEt2 (14.00 mmol, 2.59 mL) The synthesis was carried out at room temperature and then at 50°C. The crude reaction mixture was loaded onto approximately 30 g of silica gel in a loader. Purify by silica gel flash chromatography (120 g, equilibrated 30% EtOAc/DCM, elution 30% (2 CV) → 100% EtOAc (20 CV)). Elutes as a broad peak. Fractions containing product were evaporated to dryness in vacuo. 1.055 g (80% yield) of a thick gummy product was obtained. MS (APCI): Formula: _{C37H51BF2N2O Calculated for 11 (} M+H) ₌ 749; Found: 749. ¹ H NMR (400MHz, TCE) δ 6.61 (s, 2H), 4.28 (t, J=4.8Hz, 4H), 3.67 (t, J=4.8Hz, 4H), 3. 59-3.48 (m, 12H), 3.47-3.38 (m, 4H), 3.27 (s, 7H), 2.75 (s, 6H), 1.97 (s, 6H) , 1.66 (s, 6H).

Compound PLC-33: bis(2-(2-(2-methoxyethoxy)ethoxy)ethyl)10-(4-(2-(4-(1,3-dioxo-9-(4-(trifluoromethyl)) phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-dimethylphenyl)-5,5-difluoro-1,3,7,9 -Tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylate Compound PLC-33.2 (0 .045 mmol, 34 mg), compound PLC-3.5 (0.07875 mmol, 45 mg), DMAP・pTsOH salt (0.090 mmol, 27 mg), and EDC・HCl (0.180 mmol, 35 mg) in a 40 mL screw cap vial. Then, it was combined using a stirrer. Dry DCM (10 mL) was added to the vial and the reaction mixture was stirred at room temperature for 90 minutes. The crude reaction mixture was loaded onto approximately 20 g of silica gel in a loader. Purified by silica gel flash chromatography (80 g, solid, equilibrated 10% EtOAc/DCM, elution 50% (2 CV) → 100% EtOAC (20 CV)). 36 mg (62% yield) of an orange solid was obtained. MS ( _APCI ): Formula: _{C70H67BF5N3O Calculated for 15 ( M} +H) = 1296; Found: 1296. ¹ H NMR (400 MHz, TCE) δ 8.69 (d, J = 7.8 Hz, 1H), 8.64 (d, J = 8.3 Hz, 1H), 8.29 (d, J = 2.2 Hz , 1H), 8.11 (d, J = 8.1Hz, 1H), 7.85 to 7.76 (m, 5H), 7.66 to 7.61 (m, 2H), 7.55 (d , J=8.6Hz, 1H), 7.41 (d, J=8.3Hz, 2H), 7.40 to 7.34 (m, 2H), 7.06 (s, 2H), 4.38 (dd, J=5.9, 3.7Hz, 4H), 4.01 (s, 2H), 3.79 to 3.72 (m, 4H), 3.68 to 3.55 (m, 12H) , 3.55-3.48 (m, 4H), 3.35 (s, 6H), 2.85 (s, 6H), 2.16 (s, 6H), 1.74 (s, 6H).

Synthesis of compound PLC-34

Compound PLC-34: bis(2-(2-(2-methoxyethoxy)ethoxy)ethyl)5,5-difluoro-10-(4-(2-(4-(9-(4-(2-(2) -(2-methoxyethoxy)ethoxy)ethoxy)phenyl)-1,3-dioxo-1H-xanteno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6- dimethylphenyl)-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8- Dicarboxylate Compound PLC-33.2 (0.045 mmol, 34 mg), Compound PLC-17.6 (0.0675 mmol, 45 mg), DMAP・pTsOH salt (0.090 mmol, 27 mg), and EDC・HCl (0. 1350 mmol, 30 mg) were combined in a 40 mL screw cap vial using a stirrer and synthesized in the same manner as above. The crude product was loaded onto approximately 20 g of silica gel in a loader. Purified by flash chromatography (80 g, solid, equilibrated 30% EtOAc/DCM, elution 30% (2 CV) → 100% EtOAc (20 CV) → isocratic 100% EtOAc (until complete elution of product)). did. Elutes as a broad peak. Fractions containing product were evaporated to dryness in vacuo. 34 mg (54% yield) of an orange solid was obtained. MS (APCI): Formula: _C76H82BF2N3O Calculated for ₁₉ (M+H) ₌ 1391; Found _{: 1391} . ^1H NMR (400MHz, TCE) δ 8.68 (d, J = 7.9Hz, 1H), 8.63 (d, J = 8.3Hz, 1H), 8.25 (d, J = 2.1Hz , 1H), 8.11 (d, J=8.2Hz, 1H), 7.78 (dd, J=8.7, 2.1Hz, 1H), 7.64 (dd, J=8.6, 2.3Hz, 4H), 7.50 (d, J = 8.6Hz, 1H), 7.44 to 7.34 (m, 3H), 7.09 (d, J = 8.7Hz, 2H), 7.06 (s, 2H), 4.38 (t, J=4.9Hz, 4H), 4.22 (t, J=4.8Hz, 2H), 4.01 (s, 2H), 3. 90 (t, J=4.8Hz, 2H), 3.76 (dt, J=5.5, 2.7Hz, 6H), 3.71-3.54 (m, 18H), 3.54-3 .49 (m, 4H), 3.38 (s, 3H), 3.35 (s, 6H), 2.85 (s, 6H), 2.16 (s, 6H), 1.74 (s, 6H).

Synthesis of compound PLC-35

Compound PLC-35.1: 2,2,2-trifluoroethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate Compound PLC-35.1 was converted to ethyl 2,4-carboxylate in the same manner as above. Dimethyl-1H-pyrrole-3-carboxylate (12.00 mmol, 2.006 g), NaH (60% mineral oil, 36.00 mmol, 1440 mg), and 2,2,2-trifluoroethane-1-ol (120. 0 mmol, 8.74 mL) at 130°C. Due to the low boiling point of the target alcohol, all solvent was evacuated and 2,2,2-trifluoroethane-1-ol (8.74 mL) was added again. Conversion could only be carried out to about 20%. The crude material was loaded onto approximately 20 g of silica gel in a loader. Purified by silica gel flash chromatography (120 g, solid, equilibrated 10% EtOAc/hexanes, elution 10% (2 CV) → 50% EtOAc/hexanes (20 CV)). Fractions containing product were evaporated to dryness in vacuo. 468 mg (18% yield) was obtained. MS ₍ APCI): Formula: Calculated for _C9H10F3NO2 (M+H) = 222; Found _{: 222} . ^1H NMR (400MHz, TCE) δ 8.12 (s, 1H), 6.42 (dd, J=2.3, 1.2Hz, 1H), 4.61 (q, J=8.6Hz, 2H ), 2.49 (s, 3H), 2.24 (d, J=1.1Hz, 3H).

Compound PLC-35.2 Bis(2,2,2-trifluoroethyl)5,5-difluoro-10-(4-hydroxy-2,6-dimethylphenyl)-1,3,7,9-tetramethyl- 5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylate Compound PLC-35.2 was prepared by the method described above and Similarly, compound PLC-35.1 (1.575 mmol, 348 mg), 4-hydroxy-2,6-dimethylbenzaldehyde (0.750 mmol, 113 mg), and pTsOH.H ₂ O (0.300 mmol, 57 mg), then From DDQ (1.275 mmol, 289 mg) and BF ₃ .OEt ₂ (9.00 mmol, 1.10 mL) in 2×Et ₃ N (6.00 mmol, 0.84 mL) and dry DCE (20 mL) at 60° C. Then, synthesis was carried out at 50°C. The crude reaction mixture was diluted 1:1 with hexane and then loaded onto approximately 30 g of silica gel in a loader. Purified by silica gel flash chromatography (220 g, solid, equilibrated 5% EtOAc/hexanes, elution 5% (2 CV) → 30% EtOAc/hexanes (10 CV)). Fractions containing product were evaporated to dryness. 208 mg (45% yield) of an orange solid was obtained. MS _{(APCI): Formula: Calculated for C27H25BF8N2O5 ( M +} H) ₌ 621; Found: 621. ^1H NMR (400MHz, TCE) δ 6.72 (s, 2H), 4.63 (q, J=8.5Hz, 4H), 2.85 (s, 6H), 2.07 (s, 6H) , 1.77 (s, 6H).

Compound PLC-38: bis(2,2,2-trifluoroethyl)10-(4-(2-(4-(1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-1H- Xantheno[2,1,9-def]isoquinoline-2(3H)-phenyl)acetoxy)-2,6-dimethylphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4l4 ,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylate Compound 35.2 (0.060 mmol, 37 mg), Compound 3. 5 (0.105 mmol, 59 mg), DMAP pTsOH salt (0.120 mmol, 35 mg) and EDC HCl (0.240 mmol, 46 mg) were combined with dry DCM (10 mL) using a stir bar in a 40 mL screw cap vial. , synthesized in a similar manner to compound 36. The solvent was evaporated and the crude reaction mixture was taken up in toluene and loaded onto approximately 20 g of silica gel in a loader. Silica gel flash chromatography (80 g, solids, equilibration 0 % EtOAc/toluene, elution 0% (2 CV) → 0% EtOAc/toluene with 0.5% EtOAc modifier). The product quickly elutes. Orange solid, 21 mg (30% yield). MS (APCI): Chemical formula: Calculated value (M+H) for C ₆₀ H ₄₁ BF ₁₁ N ₃ O ₉ = 1168; Actual value: 1168. ¹ H NMR (400 MHz, TCE) δ 8.69 (d, J=7.9Hz, 1H), 8.64 (d, J=8.3Hz, 1H), 8.29 (d, J=2.2Hz, 1H), 8.11 (d, J= 8.1Hz, 1H), 7.85 to 7.76 (m, 5H), 7.68 to 7.61 (m, 2H), 7.55 (d, J = 8.7Hz, 1H), 7. 40 (s, 0H), 7.40-7.35 (m, 2H), 4.63 (q, J=8.5Hz, 4H), 4.02 (s, 2H), 2.86 (s, 6H), 2.16 (s, 6H), 1.76 (s, 6H).

Synthesis of compound PLC-36

Compound PLC-36.1: tert-butyl 4-(2-(3-hydroxypropyl)-1,3-dioxo-2,3-dihydro-1H-xantheno[2,1,9-def]isoquinoline-9- Compound 27.1 (1.30 mmol, 552 mg), (4- It was synthesized from (tert-butoxycarbonyl)phenyl)boronic acid (2.60 mmol, 577 mg), K ₂ CO ₃ (3.575 mmol, 494 mg) and Pd(dppf)Cl ₂ (0.0910 mmol, 67 mg) at 80°C. After adding water, the product was filtered off and washed with water and then with methanol. The compound was dried by suction and then in vacuo. 633 mg (93% yield) of a tan solid was obtained. MS ₍ APCI): Formula: Calculated for _C32H27NO6 (M+H) ₌ 522; Found: 522. ^1H NMR (400MHz, TCE) δ 8.66 (d, J = 7.9Hz, 1H), 8.61 (d, J = 8.3Hz, 1H), 8.27 (d, J = 2.2Hz , 1H), 8.13 (d, J = 8.0Hz, 2H), 8.06 (d, J = 7.9Hz, 1H), 7.80 (dd, J = 8.6, 2.1Hz, 1H), 7.74 (d, J=8.0Hz, 2H), 7.51 (d, J=8.6Hz, 1H), 7.37 (d, J=8.3Hz, 1H), 4. 33 (t, J = 6.0Hz, 2H), 3.57 (q, J = 6.0Hz, 2H), 3.20 (t, J = 6.9Hz, 1H), 2.07 to 1.91 (m, 2H), 1.64 (s, 9H).

Compound 36.2: tert-butyl 4-(2-(3-bromopropyl)-1,3-dioxo-2,3-dihydro-1H-xantheno[2,1,9-def]isoquinolin-9-yl) Benzoate A 100 mL 2N round bottom flask was placed in an aluminum heat block and equipped with a stir bar. The flask was fitted with a finned condenser/gas adapter and a flow control valve. The system was flushed with argon. To the flask was added compound PLC-36.1 (1.208 mmol, 630 mg) and dry DCM (30 mL). While stirring at room temperature under argon, Et ₃ N (2.416 mmol, 0.337 mL) was added followed by PBr ₃ (0.046 mL). The reaction mixture was stirred at room temperature for 15 minutes. _PBr3 (2.416 mmol, 0.230 mL) was added to the flask and stirring was continued at room temperature for 2 hours. The crude reaction mixture was partitioned between DCM (50 mL) and water (25 mL). 10 mL of brine was added to break the emulsion and the layers were separated. The reaction mixture was acidified with AcOH, then the reaction mixture was extracted with DCM (3 x 50 mL). The combined organic layers were dried with _MgSO4 , filtered and evaporated to dryness in vacuo. The crude product was dissolved in DCM and loaded onto approximately 20 g of silica gel in a loader. Purified by silica gel flash chromatography (80 g, solid, equilibrated 0% EtOAc/DCM, elution 0% (2 CV) → 10% EtOAc/DCM (20 CV)). Fractions containing product were evaporated to dryness in vacuo. A yellow solid, 192 mg, 27% yield was obtained. Most of the starting material becomes unknown by-products. MS ( _APCI ): Formula: Calculated for _C32H26BrNO5 (M+H) = 584; Found: ₅₈₄ . ^1H NMR (400MHz, TCE) δ 8.64 (d, J = 7.9Hz, 1H), 8.59 (d, J = 8.3Hz, 1H), 8.27 (d, J = 2.2Hz , 1H), 8.17 to 8.09 (m, 2H), 8.05 (d, J = 8.0Hz, 1H), 7.80 (dd, J = 8.6, 2.1Hz, 1H) , 7.77-7.69 (m, 2H), 7.50 (d, J = 8.6Hz, 1H), 7.36 (d, J = 8.3Hz, 1H), 4.31 (t, J=7.1Hz, 2H), 3.54 (t, J=6.8Hz, 2H), 2.34 (p, J=6.9Hz, 2H), 1.64 (s, 9H).

Compound PLC-36.3 tert-butyl 4-(2-(3-(4-formyl-3,5-dimethylphenoxy)propyl)-1,3-dioxo-2,3-dihydro-1H-xanteno[2, 1,9-def]isoquinolin-9-yl)benzoate Compound PLC-36.3 was prepared in a similar manner as compound 34.4 to compound PLC-36.2 (0.1540 mmol, 90 mg) in dry DMF (10 mL). ), 4-hydroxy-2,6-dimethylbenzaldehyde (0.308 mmol, 46 mg), and K ₂ CO ₃ . The crude reaction was diluted with crushed ice (approximately 100 g). After everything was dissolved, the crude product was filtered off and washed with water. The product was dried by suction, then dissolved in DCM and evaporated to dryness in vacuo. A quantitative yield of a yellow solid was obtained. MS (APCI): Formula: Calculated for _C41H35NO7 ( _M +H) = 654; Found: ₆₅₄ . ^1H NMR (400MHz, TCE) δ 10.43 (s, 1H), 8.65 (d, J=7.9Hz, 1H), 8.59 (d, J=8.3Hz, 1H), 8. 28 (d, J = 2.1 Hz, 1H), 8.16 to 8.10 (m, 2H), 8.07 (d, J = 8.0Hz, 1H), 7.80 (dd, J = 8 .6, 2.1Hz, 1H), 7.78-7.70 (m, 2H), 7.37 (d, J=8.4Hz, 1H), 6.55 (s, 2H), 4.39 (t, J=7.0Hz, 2H), 4.18 (t, J=6.0Hz, 2H), 2.56 (s, 6H), 2.26 (p, J=6.5Hz, 2H) , 1.64 (s, 9H).

Compound PLC-36: Diethyl 10-(4-(3-(9-(4-(tert-butoxycarbonyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinoline-2 (3H)-yl)propoxy)-2,6-dimethylphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylate Compound PLC-36 was added to compound PLC-36.3 (0.154 mmol, 100 mg), dry DCE in the same manner as above. Ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (0.308 mmol, 52 mg) in (20 mL) followed by room temperature TFA (0.020 mL) then DDQ (0.262 mmol, 59 mg), 2 Synthesized from ×Et ₃ N (1.232 mmol, 0.17 mL) and BF ₃ .OEt ₂ (1.848 mmol, 0.23 mL). The crude reaction mixture was diluted with hexane and loaded onto approximately 20 g of silica gel in a loader. Purified by silica gel flash chromatography (120 g, solids, equilibrated 0% EtOAc/toluene, elution 0% (2 CV) → 1% EtOAc/toluene (30 CV)). Partial separation only. Fractions containing pure product were evaporated to dryness in vacuo. 56 mg (36% yield) of pure product was obtained. MS ( _APCI ): Formula: _C59H56BF2N3O Calculated for ₁₀ ( _M +H) ₌ 1016; Found: 1016. ^1H NMR (400MHz, TCE) δ 8.66 (d, J = 7.9Hz, 1H), 8.60 (d, J = 8.3Hz, 1H), 8.29 (d, J = 2.1Hz , 1H), 8.16 to 8.10 (m, 2H), 8.08 (d, J = 8.0Hz, 1H), 7.80 (dd, J = 8.6, 2.1Hz, 1H) , 7.75 (d, J = 8.3 Hz, 2H), 7.51 (d, J = 8.6 Hz, 1H), 7.38 (d, J = 8.3 Hz, 1H), 6.67 ( s, 2H), 4.42 (t, J = 7.1Hz, 2H), 4.27 (q, J = 7.1Hz, 4H), 4.17 (t, J = 6.1Hz, 2H), 2.82 (s, 6H), 2.28 (p, J=6.3Hz, 2H), 2.04 (s, 6H), 1.72 (s, 6H), 1.64 (s, 9H) , 1.34 (t, J=7.1Hz, 6H).

Synthesis of compound PLC-37

Compound PLC-37.1: 2-Ethylhexyl-2,4-dimethyl-1H-pyrrole-3-carboxylate 100 mL of 2N RBF was equipped with a stirrer, a gas adapter/finned condenser, and a flow controller. The system was flushed with argon. NaH (60% mineral oil, 36.00 mmol, 1440 mg) was added to the flask. The mixture was stirred at room temperature and 2-ethylhexan-1-ol (120.00 mmol, 18.8 mL) was carefully added. When hydrogen gas evolution stopped, ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (12.00 mmol, 2.006 g) was added. The system was closed and stirred under an argon atmosphere. The heat block was set at 130° C., the reaction mixture was stirred at this temperature, and the vent was opened for 30 minutes. The vent was closed and the system was heated to 130° C. for 2 hours, then the vent was opened again for about 30 minutes. The system was heated again for about 2 hours and there was no remaining ethyl ester by LCMS. The reaction mixture was cooled to room temperature, quenched with saturated NH ₄ Cl solution, then diluted with water (approximately 100 mL). The mixture was extracted with DCM (1 x 100 mL, 2 x 50 mL). The combined organic layers were dried with _MgSO4 , filtered and evaporated to dryness in vacuo. A dark brown oil was obtained. The vial was heated at 140° C. under a flow of argon to remove excess alcohol. 2.920 g (97% yield) of brown oil was obtained. MS (APCI): Formula: Calculated for _C15H25NO2 ( _M +H) = 252; Found: ₂₅₂ . ^1H NMR (400MHz, TCE) δ 4.20-4.05 (m, 2H), 3.53 (d, J = 4.9Hz, 2H), 2.49 (s, 3H), 2.24 ( d, J = 1.0Hz, 3H), 1.75 to 1.56 (m, 4H), 1.52 to 1.16 (m, 17H), 1.00 to 0.79 (m, 13H).

Compound PLC-37.2: bis(2-ethylhexyl)5,5-difluoro-10-(4-hydroxy-2,6-dimethylphenyl)-1,3,7,9-tetramethyl-5H-4l4,5l4 -dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-dicarboxylate Compound PLC-37.2 was converted to compound PLC-37.2 in the same manner as compound 32. 37.1 (4.20 mmol, 1056 mg), 4-hydroxy-2,6-dimethylbenzaldehyde (2.00 mmol, 300 mg), and TFA (0.200 mL), then DDQ (3.40 mmol, 772 mg) and 2xEt Synthesized from BF ₃ .OEt ₂ (24.00 mmol, 3.0 mL) in ₃ N (16.00 mmol, 2.20 mL) and dry DCE (20 mL) at room temperature and then at 50 °C. The crude reaction mixture was loaded onto approximately 65 g of silica gel in a loader. Purify by silica gel flash chromatography (220 g, equilibrated 0% EtOAc/hexanes, elution 0% (2 CV) → 20% EtOAc/hexanes (30 CV)). Fractions containing product were evaporated to dryness in vacuo. 614 mg (45% yield) of a thick gummy product was obtained. MS _{(APCI): Formula: Calcd for C39H55BF2N2O5 ( M +} H) = 681; Found _: 681. ¹ H NMR (400MHz, TCE) δ 6.71 (s, 2H), 4.24-4.07 (m, 4H), 2.84 (s, 6H), 2.07 (s, 6H), 1 .75 (s, 6H), 1.48-1.22 (m, 16H), 0.96-0.82 (m, 10H).

Compound PLC-37: bis(2-ethylhexyl)10-(4-(2-(4-(1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-1H-xanteno[2,1, 9-def]isoquinolin-2(3H)-yl)phenyl)acetoxy)-2,6-dimethylphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo [1,2-c:2',1'-f][1,3,2]diazaborinine-2,8-carboxylate Compound PLC-37.2 (0.075 mmol, 51 mg), Compound PLC-3.5 (0.113 mmol, 64 mg), DMAP·pTsOH salt (0.150 mmol, 44 mg), and EDC·HCl (0.300 mmol, 58 mg) were combined in a 40 mL screw cap vial using a stir bar. Dry DCM (10 mL) was added to the vial and the reaction mixture was stirred at room temperature for 90 minutes. The crude reaction mixture was loaded onto approximately 20 g of silica gel in a loader. Purified by silica gel flash chromatography (220 g, solids, equilibrated 10% EtOAc/hexanes, elution 10% (2 CV) → 50% EtOAC/hexanes (20 CV)). 69 mg (75% yield) of an orange solid was obtained. MS _{( APCI} ): Formula: Calculated _{for C72H71BF5N3O9 (} M+H) = 1229; _Found : 1229. ^1H NMR (400MHz, TCE) δ 8.69 (d, J = 7.9Hz, 1H), 8.64 (d, J = 8.3Hz, 1H), 8.29 (d, J = 2.2Hz , 1H), 8.11 (d, J = 8.1Hz, 1H), 7.85-7.77 (m, 5H), 7.67-7.62 (m, 2H), 7.55 (d , J=8.6Hz, 1H), 7.42 (d, J=8.3Hz, 1H), 7.40 to 7.35 (m, 2H), 7.07 (s, 2H), 4.23 ~4.08 (m, 4H), 4.02 (s, 2H), 2.85 (s, 6H), 2.16 (s, 6H), 1.74 (s, 6H), 1.69 ~ 1.56 (m, 2H), 1.48-1.22 (m, 16H), 0.95-0.80 (m, 12H).

Synthesis of compound PLC-38

Compound PLC-38.1: 9-(4-butylphenyl)-2-(3-hydroxypropyl)-1H-xanteno[2,1,9-def]isoquinoline-1,3(2H)-dione Compound PLC- 38.1 was prepared in a similar manner as compound 32.2 with compound PLC-27.1 (1.500 mmol, 636 mg), (4-butylphenyl) in THF (30 mL)/DMF (6 mL)/water (3 mL). ) Synthesized from boronic acid (3.00 mmol, 534 mg), K ₂ CO ₃ (4.125 mmol, 570 mg), and Pd(dppf)Cl ₂ (0.105 mmol, 77 mg) at 80°C. The precipitated compound was filtered off, washed with water and dried in vacuo. 655 mg (92% yield) of a tan solid was obtained. MS (APCI): Formula: Calculated for _C31H27NO4 ( _M +H) ₌ 478; Found: 478. ^1H NMR (400MHz, TCE) δ 8.66 (d, J = 7.9Hz, 1H), 8.61 (d, J = 8.4Hz, 1H), 8.26 (d, J = 2.1Hz , 1H), 8.06 (d, J = 8.0Hz, 1H), 7.79 (dd, J = 8.6, 2.1Hz, 1H), 7.61 (d, J = 7.9Hz, 2H), 7.48 (d, J = 8.6Hz, 1H), 7.41-7.30 (m, 3H), 4.34 (t, J = 6.1Hz, 2H), 3.57 ( q, J = 6.0Hz, 2H), 3.24 (t, J = 6.9Hz, 1H), 2.70 (t, J = 7.7Hz, 2H), 2.06 to 1.92 (m , 2H), 1.75 to 1.64 (m, 2H), 1.42 (h, , J = 7.4Hz, 2H), 0.98 (t, J = 7.3Hz, 3H).

Compound PLC-38.2: 3-(9-(4-butylphenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)propyl 4-methyl Benzene Sulfonate A 100 mL 2N round bottom flask was placed in an aluminum heat block and equipped with a stir bar. The flask was fitted with a finned condenser/gas adapter and a flow control valve. The system was flushed with argon. To the flask were added compound PLC-38.1 (0.325 mmol, 155 mg), 4-methylbenzenesulfonic anhydride (1.30 mmol, 424 mg), and dry DCE (20 mL). The reaction mixture was stirred at room temperature under argon and Et ₃ N (1.463 mmol, 0.20 mL) was added. The reaction mixture was stirred under argon, the heat block was set at 90° C., and stirred at this temperature for 1 hour. The reaction was cooled to room temperature and loaded onto approximately 15 g of silica gel in a loader. Purified by silica gel flash chromatography (80 g, solid, equilibrated 0% EtOAc/DCM, elution 0% (2 CV) → 10% EtOAc/DCM (10 CV)). Fractions containing product were evaporated to dryness in vacuo. A yellow solid, 157 mg (77% yield) was obtained. MS ₍ APCI): Formula: Calculated for _C38H33NO6S (M+H) ₌ 632; Found: 632. ^1H NMR (400MHz, TCE) δ 8.61 (d, J = 7.9Hz, 1H), 8.56 (d, J = 8.4Hz, 1H), 8.24 (d, J = 2.2Hz , 1H), 8.04 (d, J = 8.1Hz, 1H), 7.81 to 7.72 (m, 3H), 7.61 (d, J = 8.1Hz, 2H), 7.47 (d, J=8.6Hz, 1H), 7.40-7.27 (m, 5H), 4.19 (dt, J=11.9, 6.6Hz, 4H), 2.70 (t, J=7.8Hz, 2H), 2.42 (s, 3H), 2.19 to 2.07 (m, 2H), 1.76 to 1.64 (m, 2H), 1.42 (h, J=7.3Hz, 2H), 0.98 (t, J=7.4Hz, 3H).

Compound PLC-38.3: 4-(3-(9-(4-butylphenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)propoxy )-2,6-dimethylbenzaldehyde Compound 46.3 was prepared as compound PLC-38.2 (0.119 mmol, 75 mg), 4-hydroxy-2,6-dimethylbenzaldehyde (0.356 mmol, 53 mg) and K ₂ CO ₃ (0.332 mmol, 46 mg). The reaction mixture was sonicated for 15 minutes and then stirred in a heat block at 65° C. for 7 hours. Heating was stopped and approximately 25 g of crushed ice was added to the reaction mixture. Water (approximately 90 mL) was added and the product was filtered off and washed with water. The product was dried by suction and then in vacuo. A yellow solid, 72 mg (100% yield) was obtained. MS (APCI): Formula: Calculated for _C40H35NO5 ( _M +H) ₌ 610; Found: 610. ^1H NMR (400MHz, TCE) δ 10.43 (s, 1H), 8.63 (d, J=7.9Hz, 1H), 8.58 (d, J=8.3Hz, 1H), 8. 25 (d, J = 2.1Hz, 1H), 8.05 (d, J = 8.0Hz, 1H), 7.78 (dd, J = 8.6, 2.1Hz, 1H), 7.61 (d, J=7.9Hz, 2H), 7.47 (d, J=8.6Hz, 1H), 7.39-7.29 (m, 3H), 6.55 (s, 2H), 4 .38 (t, J=7.1Hz, 2H), 4.17 (t, J=6.0Hz, 2H), 2.70 (t, J=7.8Hz, 2H), 2.56 (s, 6H), 2.26 (p, J=6.7Hz, 2H), 1.67 (p, J=7.6Hz, 2H), 1.42 (h, J=7.4Hz, 2H), 0. 98 (t, J=7.3Hz, 3H).

Compound PLC-38: diethyl 10-(4-(3-(9-(4-butylphenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl ) propoxy)-2,6-dimethylphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f ][1,3,2]Diazaborinine-2,8-dicarboxylate Compound PLC-38 was prepared in the same manner as compound 32, compound PCL-38.3 (0.118 mmol, 72 mg), and dry DCE (20 mL). of ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (0.307 mmol, 51 mg) followed by TFA (1% vol/vol) then DDQ (0.201 mmol, 46 mg), 2x _Et3 It was synthesized from N (0.944 mmol, 0.130 mL) and BF ₃ .OEt ₂ (1.420 mmol, 0.175 mL) at 80°C and then at 50°C. The crude reaction mixture was loaded onto approximately 20 g of silica gel in a loader. Purified by flash chromatography on silica gel (80 g, solid, equilibrated 0% EtOAc/hexanes, elution 0% (2 CV) → 50% EtOAc/hexanes (30 CV)). Fractions containing product were evaporated to dryness in vacuo. 21 mg (18% yield) of an orange solid was obtained. MS (APCI): Formula: Calculated for _{C58H56BF2N3O8} ( _M +H) ₌ 972; _{Found :} 972. ^1H NMR (400MHz, TCE) δ 8.65 (d, J = 7.9Hz, 1H), 8.59 (d, J = 8.4Hz, 1H), 8.26 (d, J = 2.1Hz , 1H), 8.07 (d, J = 8.1Hz, 1H), 7.78 (dd, J = 8.6, 2.1Hz, 1H), 7.65 to 7.57 (m, 2H) , 7.48 (d, J = 8.6 Hz, 1H), 7.37 (d, J = 8.6 Hz, 1H), 7.34 (d, J = 8.2 Hz, 2H), 6.67 ( s, 2H), 4.42 (t, J = 7.1Hz, 2H), 4.27 (q, J = 7.1Hz, 4H), 4.17 (t, J = 6.2Hz, 2H), 2.82 (s, 6H), 2.70 (t, J=7.7Hz, 2H), 2.34 to 2.23 (m, 2H), 2.04 (s, 6H), 1.77 to 1.62 (m, 8H), 1.42 (h, J = 7.4Hz, 2H), 1.34 (t, J = 7.1Hz, 6H), 0.98 (t, J = 7.3Hz , 3H).

Synthesis of compound PLC-39

Compound PLC-39.2: 4-(3-(9-(tert-butyl)-1,3-dioxo-1H-xanteno[2,1,9-def]isoquinolin-2(3H)-yl)propoxy) -2,6-dimethylbenzaldehyde Compound PLC-39.2 was prepared as compound 39.1 (0.601 mmol, 279 mg), 4-hydroxy-2,6-dimethylbenzaldehyde (1.802 mmol, 270 mg) in dry DMF (15 mL). ), and K ₂ CO ₃ (1.682 mmol, 232 mg). The reaction mixture was sonicated for 15 minutes and then stirred in a heat block at 65° C. for 7 hours. The crude reaction was diluted with approximately 100 mL of water and the product was filtered off. The crude precipitate was dissolved in DCM and evaporated to dryness in vacuo. The product was dissolved in DCM and loaded onto approximately 20 g of silica gel in a loader. Purified by silica gel flash chromatography (40 g, solid, equilibrated 0% EtOAc/DCM, elution 0% (2 CV) → 10% EtOAc/DCM (20 CV)). Fractions containing product were evaporated to dryness in vacuo. A yellow solid, 301 mg (94% yield) was obtained. MS (APCI): Formula: Calculated for _C34H31NO5 (M+ _H ) = 534; Found: ₅₃₄ . ^1H NMR (400MHz, TCE) δ 10.43 (s, 1H), 8.63 (d, J=7.9Hz, 1H), 8.57 (d, J=8.4Hz, 1H), 8. 06 (d, J=2.3Hz, 1H), 8.01 (d, J=8.0Hz, 1H), 7.62 (dd, J=8.8, 2.3Hz, 1H), 7.37 (d, J=8.7Hz, 1H), 7.33 (d, J=8.3Hz, 1H), 6.56 (s, 2H), 4.38 (t, J=7.0Hz, 2H) , 4.17 (t, J=6.0Hz, 2H), 2.57 (s, 6H), 2.25 (q, J=6.6Hz, 2H), 1.44 (s, 9H).

Compound PLC-39: diethyl 10-(4-(3-(9-(4-(tert-butyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinoline-2( 3H)-yl)propoxy)-2,6-dimethylphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2', 1'-f][1,3,2]diazaborinine-2,8-dicarboxylate Compound PLC-39 was added to compound PLC-39.2 (0.275 mmol, 147 mg) and dried in the same manner as compound 32. Ethyl 2,4-dimethyl-1H-pyrrole-3-carboxylate (0.413 mmol, 69 mg) in DCE (40 mL) followed by pTsOH.H ₂ O (0.110 mmol, 21 mg) then DDQ (0.468 mmol , 106 mg), 2×Et ₃ N (2.20 mmol, 0.31 mL) and BF ₃ .OEt ₂ (3.30 mmol, 0.41 mL). The crude reaction mixture was diluted with hexane and loaded onto approximately 20 g of silica gel in a loader. Purified by silica gel flash chromatography (120 g, solids, equilibrated 0% EtOAc/DCM, elution 0% (2 CV) → 10% EtOAc/DCM (50 CV)). Fractions containing product were evaporated to dryness in vacuo. 71 mg (29% yield) of an orange solid was obtained. MS (APCI): Formula: Calculated for _{C58H56BF2N3O8} ( _M +H) ₌ 972; _{Found :} 972. ^1H NMR (400MHz, TCE) δ 8.65 (d, J = 7.9Hz, 1H), 8.58 (d, J = 8.4Hz, 1H), 8.07 (d, J = 2.3Hz , 1H), 8.03 (d, J=8.1Hz, 1H), 7.62 (dd, J=8.7, 2.2Hz, 1H), 7.36 (d, J=8.7Hz, 1H), 7.33 (d, J = 8.3Hz, 1H), 6.68 (s, 2H), 4.42 (t, J = 7.0Hz, 2H), 4.28 (q, J = 7.1Hz, 4H), 4.16 (t, J = 6.2Hz, 2H), 2.83 (s, 6H), 2.28 (p, J = 5.8Hz, 2H), 2.05 ( s, 6H), 1.72 (s, 6H), 1.44 (s, 9H), 1.34 (t, J=7.1Hz, 6H).

Synthesis of compound PLC-40

Compound PLC-40.1: 9-(6-(2-amino-4-(tert-butyl)phenoxy)-2-(2-hydroxyethyl)-1H-benzo[de]isoquinoline-1,3(2H) -dione Compound PLC-40.1 was added to compound PLC-4.2 (8.827 mmol, 3.190 g), ethanolamine (17.65 mmol, 1.066 mL), and DMAP (2. 648 mmol, 324 mg) followed by 200 proof ethanol (70 mL). The crude precipitate was filtered off, dissolved in acetone and evaporated to dryness in vacuo. A tan solid, 2.777 g (78% yield). MS (APCI): Chemical formula: Calculated value for C ₂₄ H ₂₄ N ₂ O ₄ (M+H) = 405; Actual value: 405. ¹ H NMR (400 MHz, TCE) δ 8.80 (dd , J=8.4, 1.2Hz, 1H), 8.67 (dd, J=7.3, 1.2Hz, 1H), 8.46 (d, J=8.3Hz, 1H), 7. 84 (dd, J=8.4, 7.3Hz, 1H), 7.02-6.92 (m, 3H), 6.87 (dd, J=8.4, 2.3Hz, 1H), 4 .42 (t, J=5.2Hz, 2H), 3.95 (t, J=5.2Hz, 2H), 3.74 (s, 2H), 2.39 (s, 1H), 1.35 (s, 9H).

Compound PLC-40.2: 9-(tert-butyl)-2-(2-hydroxyethyl)-1H-xanteno[2,1,9-def]isoquinoline-1,3(2H)-dione Compound PLC-40 .2 was prepared in the same manner as above using compound PLC-40.1 (6.863 mmol, 2.776 g), NaNO ₂ (51.475 mmol, 3.552 g), concentrated HCl (34.317 mmol, 2.83 mL). , and CuSO ₄ .5H ₂ O (46.67 mmol, 11.653 g). The crude product was approximately 10% acetate. This was cleaved with K ₂ CO ₃ similarly to compound 52.2. The crude cleavage mixture was dissolved in acetone and evaporated onto approximately 20 g of silica gel and placed into a loader. Purified by silica gel flash chromatography (120 g, solid, equilibrated 0% EtOAc/DCM, elution (2 CV) → 85% EtOAc/DCM (20 CV)). Fractions containing product were evaporated to dryness in vacuo. 732 mg (27% yield) of a yellow solid was obtained. MS (APCI): Formula: Calculated for _C24H21NO4 ( _M +H) ₌ 388; Found: 388.

Compound PLC-40.3: 2-(2-bromoethyl)-9-(tert-butyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione Compound PLC-40. 3 was prepared in a similar manner as compound 50.3 with compound PLC-40.2 (1.884 mmol, 730 mg), perbromomethane (2.826 mmol, 937 mg) and PPh ₃ (2. 826 mmol, 741 mg). The crude reaction mixture was loaded onto approximately 30 g of silica gel in a loader. Purified by silica gel flash chromatography (120 g, solids, equilibrated 0% EtOAc/DCM, elution 0% (2 CV) → 15% EtOAc/DCM (20 CV)). Fractions containing product were evaporated to dryness in vacuo. 556 mg (44% yield) of a yellow solid was obtained. NMR shows only about 50% purity. MS ( _APCI ): Formula: Calculated for _C24H20BrNO3 (M+H) = 450; Found _: 450. ^1H NMR (400MHz, TCE) δ 8.62 (d, J = 7.9Hz, 1H), 8.57 (d, J = 8.4Hz, 1H), 8.04 (d, J = 2.3Hz , 1H), 7.98 (d, J = 8.0Hz, 1H), 7.62 (dd, J = 8.7, 2.2Hz, 1H), 7.35 (d, J = 8.7Hz, 1H), 7.31 (d, J = 8.4Hz, 1H), 4.58 (t, J = 7.6Hz, 2H), 3.73 to 3.65 (m, 2H), 1.44 ( s, 9H).

Compound PLC4.4: 4-(2-(9-(tert-butyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)ethoxy)-2 ,6-dimethylbenzaldehyde Compound PLC-40.4 was prepared as described above in a similar manner to compound PLC-40.3 (0.450 mmol, 203 mg), 4-hydroxy-2,6-dimethyl in dry DMF (10 mL). It was synthesized from benzaldehyde (1.350 mmol, 203 mg) and K ₂ CO ₃ (1.260 mmol, 174 mg). The crude product was filtered off, washed with water, dissolved in DCM and evaporated to dryness. Dissolved in DCM and evaporated onto approximately 20 g of silica gel and placed in a loader. Purified by silica gel flash chromatography (120 g, solids, equilibrated 0% EtOAc/DCM, elution 0% (2 CV) → 15% EtOAc/DCM (20 CV)). Fractions containing product were evaporated to dryness. The reaction was carried out again in the same manner. Both purified products were combined to give 64 mg of yellow solid (13% yield). MS (APCI): Formula: Calculated for _C33H29NO5 ( _M +H) = 520; Found: ₅₂₀ . ^1H NMR (400MHz, TCE) δ 10.41 (s, 1H), 8.66 (d, J=7.9Hz, 1H), 8.60 (d, J=8.3Hz, 1H), 8. 06 (d, J=2.2Hz, 1H), 8.01 (d, J=8.0Hz, 1H), 7.62 (dd, J=8.7, 2.2Hz, 1H), 7.36 (d, J=8.7Hz, 1H), 7.33 (d, J=8.4Hz, 1H), 6.66 (s, 2H), 4.64 (t, J=6.2Hz, 2H) , 4.37 (t, J=6.2Hz, 2H), 2.57 (s, 6H), 1.44 (s, 9H).

Compound PLC-40: Diethyl 10-(4-(2-(9-(tert-butyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl) ethoxy)-2,6-dimethylphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f] [1,3,2]Diazaborinine-2,8-carboxylate Compound PLC-40 was prepared in a manner similar to the method described above, including compound PLC-40.4 (0.121 mmol, 63 mg), ethyl in dry DCE (20 mL). 2,4-dimethyl-1H-pyrrole-3-carboxylate (0.263 mmol, 44 mg), followed by pTsOH.H ₂ O (0.0182 mmol, 4 mg), then DDQ (0.158 mmol, 36 mg), 2x Synthesized from Et ₃ N (0.970 mmol, 0.140 mL) and BF ₃ .OEt ₂ (1.455 mmol, 0.180 mL). The crude reaction mixture was loaded onto approximately 20 g of silica gel in a loader. Purified by silica gel flash chromatography (120 g, solid, equilibrated 0% EtOAc/hexanes, elution 0% (2 CV) → 75% EtOAc/hexanes (30 CV)). Fractions containing product were evaporated to dryness in vacuo. 78 mg (73% yield) of an orange solid was obtained. MS ₍ APCI): Formula: Calculated for _{C51H50BF2N3O8} (M+H) ₌ 882; _{Found :} 882. ^1H NMR (400MHz, TCE) δ 8.68 (d, J = 7.9Hz, 1H), 8.62 (d, J = 8.3Hz, 1H), 8.07 (d, J = 2.3Hz , 1H), 8.03 (d, J = 8.1Hz, 1H), 7.63 (dd, J = 8.8, 2.2Hz, 1H), 7.36 (t, J = 8.9Hz, 2H), 6.78 (s, 2H), 4.66 (t, J = 6.5Hz, 2H), 4.35 (t, J = 6.4Hz, 2H), 4.25 (q, J = 7.1Hz, 4H), 2.81 (s, 6H), 2.05 (s, 6H), 1.67 (s, 6H), 1.44 (s, 9H), 1.32 (t, J =7.1Hz, 6H).

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, such as PLC-1 or PLC-2, 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 samples were 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 spectra obtained for PCL-1 are shown in FIGS. 1 and 2, and the absorption/emission spectra obtained for PCL-2 are shown in FIG. 3.

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 (21)

A photoluminescent complex,
A blue light absorbing part,
a linker complex;
a boron-dipyrromethene (BODIPY) moiety;
including;
the photoluminescent complex absorbs light energy at a first excitation wavelength and emits light energy at a second higher wavelength; the photoluminescent complex has an emission quantum yield of greater than 80%; Complex. 2. The photoluminescent complex of claim 1, wherein the blue light absorbing moiety is a xanthenoisoquinoline derivative. The xanthenoisoquinoline derivative has the general formula:

(wherein each R ⁰ is independently hydrogen (H), a C ₁ -C ₄ alkyl group, a trifluoromethyl group, an optionally substituted aryl group, or an alkoxy group, and R ¹⁰ is hydrogen ( H), a C ₁ -C ₄ alkyl group, an optionally substituted aryl group, -(OCH ₂ CH ₂ ) _n -OCH ₃ , or an alkoxy group, where n is 1, 2, 3 or 4, and the above-mentioned An optionally substituted aryl group is unsubstituted phenyl,

3. The photoluminescent complex according to claim 2, which is 2. The photoluminescent complex of claim 1, wherein the blue light absorbing moiety is a naphthalimide derivative. The naphthalimide derivative has the general formula:

(wherein each R ⁰ is independently hydrogen (H), a C ₁ -C ₄ alkyl group, a trifluoromethyl group, an optionally substituted aryl group, or an alkoxy group, and R ¹⁰ is hydrogen ( H), a C ₁ -C ₄ alkyl group, a trifluoromethyl group, an optionally substituted aryl group, -(OCH ₂ CH ₂ ) _n -OCH ₃ , or an alkoxy group, where n is 1, 2, 3 or 4, and the optionally substituted aryl group is unsubstituted phenyl,

5. The photoluminescent complex according to claim 4, which is The BODIPY portion has the general formula:

(wherein R ¹ and R ⁶ are independently selected from hydrogen (H), an alkyl group, or an alkene group, and R ³ and R ⁴ are independently selected from C ₁ -C ₂ alkyl) , R ² and R ⁵ are independently hydrogen (H), alkyl, cyano (-CN), -C(=O)-(OCH ₂ CH ₂ ) _n -OCH ₃ , alkyl ester, fluoroalkyl ester, or aryl ester, n is 1, 2, 3 or 4;
R ⁷ and R ⁸ are independently selected from hydrogen (H), a methyl group, a halide, or a C ₁ -C ₃ alkoxy group;
2. The photoluminescent complex of claim 1, wherein L is a linker complex. 7. The photoluminescent complex of claim 6, wherein R ¹ , R ³ , R ⁴ , and R ⁶ are independently C ₁ -C ₃ alkyl groups, and R ⁷ and R ⁸ are methyl groups. R ² and R ⁵ are independently,

The photoluminescent complex according to claim 6, which is 7. The photoluminescent complex according to claim 6, wherein the linker complex L is an unsubstituted ester moiety, a substituted ester moiety, or an ether moiety. L is

The photoluminescent complex according to claim 9. L is

The photoluminescent complex according to claim 9. L is

The photoluminescent complex according to claim 9. The photoluminescent complex has the following structure:

13. A photoluminescent complex according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, comprising one of: A color conversion film,
a transparent base material layer;
a color conversion layer including a resin matrix;
a photoluminescent complex comprising 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, further comprising a singlet oxygen quencher. 15. The color conversion film of claim 14, further comprising a free radical scavenger. 15. The color conversion film of claim 14, wherein the color conversion film has a thickness of between 10 [mu]m and 200 [mu]m. 15. The color conversion film of claim 14, wherein the color conversion film absorbs light in a wavelength range of about 400 nm to about 480 nm and emits light in a wavelength range of 500 nm to about 560 nm. A method for producing a color conversion film according to claim 14, 15, 16, 17 or 18, comprising:
Dissolving the photoluminescent complex and binder resin according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14 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, 16, 17 or 18. A display device comprising a backlight unit according to claim 20.