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

Abstract

The present disclosure relates to yeast cells that have been genetically modified to reduce the tendency to degrade certain platform chemicals, such as acrylic acid, and methods for preparing and using such yeast cells for the production of acrylic acid and other compounds. The present disclosure relates to a novel photoluminescent complex comprising a BODIPY moiety, a blue light absorbing moiety, and a linker conjugate, wherein the linker conjugate covalently bonds the blue light absorbing moiety to the ring-locked BODIPY moiety, a color conversion film comprising the photoluminescent complex, and a backlight unit using the same.

Description

[Technical Field]

[0001] [CROSS-REFERENCE TO RELATED APPLICATIONS] This application claims priority to U.S. Provisional Patent Application No. 63 / 248,863, filed September 27, 2021, and U.S. Provisional Patent Application No. 63 / 278,944, filed November 12, 2021, the entire disclosures of which are incorporated herein by reference. [Background technology]

[0002] Unless otherwise indicated in this disclosure, the details described in this disclosure are not prior art to the claims of this application and are not admitted to be prior art by inclusion in this section.

[0003] In color reproduction, a gamut, or color gamut, is a particular complete subset of colors available on a device such as a television or monitor. For example, Adobe™ Red Green Blue (RGB), a wide-gamut color space achieved by using pure spectral primaries, was developed to provide a wider color gamut and result in a more realistic representation of visible colors viewed through a display. It is believed that devices that can provide a wider color gamut may enable displays to depict more vibrant colors.

[0004] As high-definition, large-screen displays become more common, the demand for higher-performance, thinner, and more functional displays is increasing. Current light-emitting diodes (LEDs) are obtained by exciting green, red, or yellow phosphors with a blue light source to produce a white light source. However, the full width at half maximum (FWHM) of the emission peaks of current green and red phosphors is very large, typically exceeding 40 nm, resulting in overlapping green and red spectra, resulting in color rendering that is completely indistinguishable from one another. This overlap leads to poor color rendering and a reduced color gamut.

[0005] To compensate for the reduced color gamut, quantum dot-containing films have been developed in combination with LEDs, but quantum dots have several drawbacks, including toxicity, low efficiency, expensive encapsulation processes, and size uniformity.

[0006] Therefore, there is a need for improved performance in color conversion films, backlight units, and display devices. Summary of the Invention

[0007] The photoluminescent complexes described herein can be used to improve the contrast between distinguishable colors in televisions, computer monitors, smart devices, and any other devices that utilize color displays. The photoluminescent complexes of the present disclosure include color conversion dye complexes that have good blue light absorption and narrow emission bandwidths, with full width at half maximum (FWHM) of the emission band less than 40 nm. In some embodiments, the photoluminescent complexes absorb light at a first wavelength and emit light at a second wavelength that is longer than the first wavelength. The photoluminescent complexes disclosed herein can be utilized in color conversion films for use in light-emitting devices. The color conversion films of the present disclosure reduce color degradation by reducing overlap in the color spectrum, resulting in high-quality color rendering.

[0008] Some embodiments include a photoluminescent complex, which may include a blue-light-absorbing naphthalimide derivative, a linker conjugate including an unsubstituted ester, a substituted ester, an unsubstituted ether, or a substituted ether, and a ring-locked boron dipyrromethene (BODIPY) moiety. In some embodiments, the linker conjugate may covalently link the naphthalimide derivative to the ring-locked BODIPY moiety. In many embodiments, the ring-locked BODIPY moiety absorbs energy from the naphthalimide derivative at a first excitation wavelength and emits light energy at a second, higher wavelength. In various embodiments, the photoluminescent complex has an emission quantum yield greater than 80%.

[0009] In some embodiments, the photoluminescent complexes can have an emission band with a full width at half maximum (FWHM) of up to 40 nm.

[0010] In many embodiments, the photoluminescent complexes can have a Stokes shift, ie, the difference between the excitation peak of the blue light absorbing moiety and the emission peak of the BODIPY moiety, of 45 nm or greater.

[0011] Many embodiments include a color conversion film, which may include a transparent substrate layer, a color conversion layer comprising a resin matrix, and at least one photoluminescent complex described herein dispersed within the resin matrix. In some embodiments, the color conversion film may have a thickness between 1 μm and about 200 μm. In many embodiments, the color conversion film of the present disclosure is capable of absorbing blue light in the range of 400 nm to about 480 nm and emitting light in the wavelength range of 510 nm to about 560 nm. Other embodiments include a color conversion film capable of absorbing blue light in the range of 400 nm to about 480 nm and emitting light in the wavelength range of 580 nm to about 670 nm. In various embodiments, the color conversion film may further include a transparent substrate layer. In some embodiments, the transparent substrate layer may have two opposing surfaces, with the color conversion layer disposed on one of the opposing surfaces.

[0012] In some embodiments, the color conversion film can further comprise a singlet oxygen quencher. In some embodiments, the color conversion film can further comprise a free radical scavenger.

[0013] Many embodiments include a method of making a color conversion film, the method comprising dissolving a photoluminescent complex described herein and a binder resin in a solvent and applying the mixture to one of the opposing surfaces of a transparent substrate.

[0014] Some embodiments include a backlight unit comprising the color conversion film described herein.

[0015] Some embodiments include a display device comprising a backlight unit as described herein.

[0016] The present application provides a photoluminescent complex having excellent color gamut and luminescence properties, a method for producing a color conversion film using the photoluminescent complex, and a backlight unit including the color conversion film. These and other embodiments are described in more detail below. [Brief explanation of the drawings]

[0017] [Figure 1] 1 is a graph showing the absorption and emission spectra of one embodiment of a photoluminescent complex (PLC-1). [Figure 2] 1 is a graph showing the absorption and emission spectra of one embodiment of a photoluminescent complex (PLC-2). [Figure 3] 1 is a graph showing the absorption and emission spectra of one embodiment of a photoluminescent complex (PLC-3). DETAILED DESCRIPTION OF THE INVENTION

[0018] The present disclosure relates to photoluminescent complexes for use in color conversion films, backlight units, and display devices containing the same. The photoluminescent complexes can be used to improve and enhance the transmittance of one or more desired emission bandwidths in the color conversion film. In some embodiments, the photoluminescent complexes can increase the transmittance of a first desired emission bandwidth while decreasing the transmittance of a second desired emission bandwidth. In some embodiments, the present disclosure describes photoluminescent complexes that can increase the contrast or intensity between two colors, enhancing their differentiation from one another.

[0019] In some embodiments, boron dipyrromethene (BODIPY) compounds are used as emissive materials to replace the use of quantum dots. BODIPY conjugates can have narrow FWHMs, high fluorescence efficiencies, stability to both moisture and oxygen, and low manufacturing costs. Current BODIPY strategies have several drawbacks, including low absorption of blue LED light (e.g., 450 nm), resulting in inefficient conversion of blue LED light to green and red light, and a wide FWHM when used in color conversion films. In some embodiments, the BODIPY compounds disclosed herein overcome these limitations.

[0020] As used herein, when a compound or chemical structure is referred to as "substituted," the compound or chemical structure can contain one or more substituents. A substituted group is derived from an unsubstituted parent structure, where one or more hydrogen atoms on the parent structure have been independently replaced by one or more substituents. In some embodiments, the substituents are independently selected from the group consisting of F, Cl, Br, I, C, and the like. 0~7 H 1~15 O 1~2 N 0~2 , C 0~7 H 1~15 O 0~2 N 1~2 , optionally substituted alkyl (including unsubstituted alkyl such as methyl, ethyl, C alkyl, C alkyl, fluoroalkyl, e.g., CF), alkenyl, or C 3~7 It may also be heteroalkyl.

[0021] As used herein, the term "alkyl" group refers to a hydrocarbon group that does not contain double or triple carbon-carbon bonds, and includes straight-chain, branched-chain, or cyclic alkyls.

[0022] An "alkene" moiety refers to a group having at least one carbon-carbon double bond (-C=C-), and includes straight-chain, branched-chain, or cyclic alkene moieties.

[0023] An "alkyne" moiety refers to a group having at least one carbon-carbon triple bond (-C≡C-), and includes straight-chain, branched-chain, or cyclic alkyne moieties.

[0024] In some embodiments, an alkyl moiety can have 1 to 6 carbon atoms, and numerical ranges such as "1 to 6" (whether they appear herein or not) refer to each integer within the given range, e.g., "1 to 6 carbon atoms" means that the alkyl group can have 1 carbon atom, 2 carbon atoms, 3 carbon atoms, etc., up to and including 6 carbon atoms, although this definition also encompasses instances of the term "alkyl" where no numerical range is specified. The alkyl groups of compounds specified herein are "C 1~6 alkyl" or similar designations. 1~6 "Alkyl" indicates that there are 1 to 6 carbon atoms in the alkyl chain, i.e., the alkyl chain can be methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl 、 sec-butyl, t-butyl, etc. Therefore, C 1~6 Examples of alkyl include C 1~2 Alkyl, C 3~4 Alkyl, C 4~5 Alkyl or C 5~6 Examples of alkyl groups include alkyl. The alkyl group can be substituted or unsubstituted. Typical alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl, hexyl, ethenyl, propenyl, butenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.

[0025] Typical alkene groups include, but are not limited to, ethenyl, propenyl, butenyl, and the like.

[0026] As used herein, the term "heteroalkyl" refers to an alkyl group, as defined herein, in which one or more member carbon and / or hydrogen atoms have been replaced by nitrogen, oxygen, or sulfur. Examples include, but are not limited to, -CH2-O-CH3, -CH2-CH2-O-CH3, -CH2-N(CH3)-CH3, -CH2-CH2-NH-CH3, -CH2-CH2-N(CH3)-CH3, -CH2-S-CH2-CH3, -CH2-NH-O-CH3, and the like.

[0027] The term "aromatic" refers to a planar ring having a delocalized π-electron system containing 4n+2 (where n is an integer) π-electrons. An aromatic ring can be formed from 5, 6, 7, 8, 9, or 10 or more atoms. An aromatic ring can be optionally substituted. The term "aromatic" includes both carbocyclic aryl (e.g., phenyl) and heterocyclic aryl (i.e., "heteroaryl" or "heteroaromatic") groups (e.g., pyridine). The term includes monocyclic or fused-ring polycyclic (i.e., rings that share adjacent pairs of carbon atoms) groups.

[0028] The term "hydrocarbon ring" refers to a monocyclic or polycyclic ring system containing only carbon and hydrogen, which may be saturated. Monocyclic carbocycles include groups having from 3 to 12 carbon atoms. Illustrative examples of monocyclic groups include the following moieties: [ka] etc.

[0029] Illustrative examples of polycyclic groups include the following moieties: [ka]

[0030] As used herein, the term "aryl" refers to an aromatic ring in which each of the atoms forming the ring is a carbon atom. The aryl ring can be formed by 5, 6, 7, 8, or more carbon atoms. The aryl group can be substituted or unsubstituted. Examples of aryl groups include, but are not limited to, phenyl, naphthalenyl, phenanthrenyl, etc.

[0031] The term "heteroaryl" refers to an aryl group containing one or more ring heteroatoms selected from nitrogen, oxygen, sulfur, or a combination thereof, wherein the heteroaryl group has 4 to 10 atoms in its ring system, provided that the ring of the group does not contain two adjacent nitrogen, oxygen, or sulfur atoms. It is understood that the heteroaryl ring may have additional heteroatoms within the ring. In heteroaryls having two or more heteroatoms, the two or more heteroatoms may be the same or different from one another. Heteroaryls can be optionally substituted. An N-containing heteroaryl moiety refers to an aryl group in which at least one of the skeletal atoms of the ring is a nitrogen atom. Illustrative examples of heteroaryl groups include the following moieties: pyrrole, imidazole, etc.

[0032] As used herein, the term "halogen" means fluorine, chlorine, bromine, and iodine.

[0033] As used herein, the terms "bond," "bonded," "direct bond," or "single bond" refer to a chemical bond between two atoms.

[0034] The term "moiety" as used herein refers to a specific segment or functional group of a molecule. A chemical moiety is often recognized as a chemical entity embedded within or added to a molecule.

[0035] As used herein, the term "cyano" or "nitrile" refers to any organic compound containing a -CN functional group.

[0036] The term "ester" refers to a chemical moiety having the formula -COOR, where R is alkyl, cycloalkyl, aryl, heteroaryl (bonded through a ring carbon), and heterocyclic (bonded through a ring carbon) moiety. Any hydroxy or carboxyl side chain on the compounds described herein may be esterified. The procedures and specific groups for making such esters can be any suitable method and can be readily found in reference sources.

[0037] As used herein, the term "ether" refers to a chemical moiety containing an oxygen atom connected to two alkyl or aryl groups having the general formula RO-R', where the terms alkyl and aryl are as defined herein.

[0038] As used herein, the term "ketone" refers to a chemical moiety containing a carbonyl group (a carbon-oxygen double bond) connected to two alkyl or aryl groups having the general formula RC(=O)R', where the terms alkyl and aryl are as defined herein.

[0039] As used herein, the term "ring-locked" refers to a chemical structure in which one or more series of atoms in a compound are joined to form a ring. The ring size can vary from three atoms to many atoms (e.g., aromatic rings, carbocyclic rings).

[0040] As used herein, the term "BODIPY" refers to a compound of the formula: [ka] refers to a chemical moiety having the formula:

[0041] BODIPY can be composed of a dipyrromethene complexed with a disubstituted boron atom, typically a BF2 unit. The IUPAC name for BODIPY is 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene.

[0042] As used herein, the term "naphthalimide" or "naphthalimide derivative" refers to a compound having the following formula: [ka] refers to a chemical moiety having the formula:

[0043] 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 light-emitting moiety and an emitting light-emitting moiety connected via a linker, the distance between which is adjusted so that the absorbing light-emitting moiety transfers its energy to an acceptor light-emitting moiety, which then emits at a second wavelength greater than the first absorbing wavelength.

[0044] Some embodiments include a photoluminescent complex. In some examples, the complex includes a blue-light-absorbing donor chromophore, the donor chromophore including a naphthalimide derivative, a linker conjugate, and a ring-locked boron dipyrromethene (BODIPY) moiety. In some embodiments, the linker conjugate can covalently link the naphthalimide derivative and the ring-locked BODIPY moiety. In some examples, the naphthalimide derivative absorbs light at a first excitation wavelength and transfers the energy to the ring-locked BODIPY moiety, which then emits light energy at a second wavelength. Energy transfer from the excited naphthalimide derivative to the ring-locked BODIPY moiety is believed to occur via Förster resonance energy transfer (FRET). This idea is based on the absorption / emission spectrum of the photoluminescent complex, which has two major absorption bands: one blue-light absorption band (naphthalimide derivative) and the other ring-locked BODIPY absorption band, and only one emission band at the emission wavelength of the BODIPY moiety (see Figures 1 and 2).

[0045] In one embodiment, the photoluminescent complex may have a high emission quantum yield. In some embodiments, the emission quantum yield may be greater than 50%, 60%, 70%, 80%, and / or 90%. In many embodiments, the emission quantum yield may be greater than 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or 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 light-emitting moiety. In various embodiments, the absorbing-light-emitting moiety may have an emission quantum yield greater than 80%. In some embodiments, the quantum yield may be greater than 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%), 0.95 (95%), 0.96 (96%), 0.97 (97%), 0.98 (98%), and may be up to nearly 100%. Quantum measurements on films may be performed by a spectrophotometer, such as a Quantaurus-QY spectrophotometer (Hamamatsu, Inc., Campbell, CA, USA).

[0046] 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. The FWHM is the width of the emission band in nanometers at an emission intensity that is half the maximum emission intensity for the band. In some embodiments, the photoluminescent complex has an emission band FWHM value of about 35 nm or less, about 30 nm or less, about 25 nm or less, or about 20 nm or less. In some embodiments, the FWHM is about 40 nm to about 35 nm, about 35 nm to about 30 nm, about 30 nm to about 25 nm, about 25 nm to about 20 nm, or less than about 20 nm.

[0047] In some embodiments, the photoluminescent complex may have a Stokes shift of 45 nm or greater. As used herein, the term "Stokes shift" refers to the distance between the excitation peak of the blue light-absorbing moiety and the emission peak of the BODIPY moiety. In some embodiments, the Stokes shift is at least 45 nm. In some embodiments, the Stokes shift of the photoluminescent complex may be about 45 nm to 50 nm, about 50 nm to 55 nm, about 55 nm to 60 nm, about 60 nm to 65 nm, about 65 nm to 70 nm, about 70 nm to 75 nm, about 75 nm to 80 nm, about 80 nm to 85 nm, about 85 nm to 90 nm, about 90 nm to 95 nm, about 95 nm to 100 nm, or greater than about 100 nm, or any number within a range bounded by any of these values.

[0048] In some embodiments, the blue light absorbing moiety may have a peak absorption maximum between wavelengths of about 400 nm and about 480 nm, in some embodiments, the peak absorption wavelength may be between about 400 nm and about 405 nm, about 405 nm and 410 nm, about 410 nm and 415 nm, about 415 nm and 420 nm, about 420 nm and 425 nm, about 425 nm and 430 nm, about 430 nm and 435 nm, about 435 nm and 440 nm, about 440 nm and 445 nm, about 445 nm and 450 nm, about 450 nm and 455 nm, about 455 nm and 460 nm, about 460 nm and 465 nm, about 465 nm and 470 nm, about 470 nm and 475 nm, about 475 nm and 480 nm, or about any wavelength within a range bounded by any of these values.

[0049] In some embodiments, the blue light absorbing moiety may have a red / orange absorption with a peak absorption maximum between wavelengths of about 580 nm and about 650 nm. In many embodiments, the peak absorption may be in the range of about 580 nm to about 585 nm, about 585 nm to 590 nm, about 590 nm to 595 nm, about 595 nm to 600 nm, about 600 nm to 605 nm, about 605 nm to 610 nm, about 610 nm to 615 nm, about 615 nm to 620 nm, about 620 nm to 625 nm, about 625 nm to 630 nm, about 630 nm to 635 nm, about 635 nm to 640 nm, about 640 nm to 645 nm, about 645 nm to 650 nm, or any wavelength within a range bounded by any of these values.

[0050] In some embodiments, the photoluminescent complex can have an emission peak between about 590 nm and about 660 nm. In many embodiments, the emission peak can be between about 590 nm to about 595 nm, about 595 nm to 600 nm, about 600 nm to 605 nm, about 605 nm to 610 nm, about 610 nm to 615 nm, about 615 nm to 620 nm, about 620 nm to 625 nm, about 625 nm to 630 nm, about 630 nm to 635 nm, about 635 nm to 640 nm, about 640 nm to 645 nm, about 645 nm to 650 nm, about 650 nm to 655 nm, about 655 nm to 660 nm, or any wavelength within a range bounded by any of these values.

[0051] Other embodiments include photoluminescent complexes in which the spatial distance between the blue-light-absorbing naphthalimide derivative and the BODIPY moiety is adjusted via a linker conjugate for improved energy transfer of the blue-light-absorbing naphthalimide derivative to the BODIPY moiety.

[0052] The present disclosure describes a photoluminescent complex (PLC) comprising a blue-light-absorbing naphthalimide derivative, a linker conjugate, and a ring-locked BODIPY moiety. The linker conjugate covalently bonds the blue-light-absorbing naphthalimide derivative and the ring-locked BODIPY moiety. In some embodiments, the naphthalimide derivative absorbs light energy at a first excitation wavelength and transfers the energy to the ring-locked BODIPY moiety, which then absorbs energy from the naphthalimide derivative and emits light energy at a second, higher wavelength. In such embodiments, the photoluminescent complex has an emission quantum yield of greater than 80%.

[0053] The linker conjugate covalently connects the blue-light-absorbing naphthalimide derivative and the ring-locked BODIPY moiety. The linker conjugate can be adjusted to control the spatial distance between the blue-light-absorbing naphthalimide derivative and the ring-locked BODIPY moiety. Adjusting the spatial distance between the ring-locked naphthalimide derivative and the ring-locked BODIPY moiety can adjust the quantum yield. In some embodiments, the distance separating the blue-light-absorbing naphthalimide derivative and the ring-locked BODIPY moiety can be about 8 Å or less. The linker conjugate can maintain the distance between the blue-light-absorbing naphthalimide derivative and the ring-locked BODIPY moiety.

[0054] In some embodiments, the photoluminescent complex comprises a linker conjugate (L) that covalently links the blue-light-absorbing naphthalimide derivative and the ring-locked BODIPY moiety. In some embodiments, the linker conjugate can comprise a single bond between the naphthalimide derivative and the ring-locked BODIPY moiety.

[0055] In some embodiments, the linker conjugate may comprise an unsubstituted ester, a substituted ester, an unsubstituted ether, or a substituted ether. In some embodiments, the linker conjugate may comprise an optionally substituted C 2~7It may contain ester groups.

[0056] Some examples include linker conjugates that include substituted ester groups, the linker conjugates having the following structure: [ka] may be selected from one of:

[0057] In some embodiments, the linker conjugate may comprise an unsubstituted ester group. When the linker conjugate comprises an unsubstituted ester group, the linker conjugate has the following structure: [ka] Contains one of the following:

[0058] In some embodiments, the linker conjugate may include unsubstituted and / or substituted ethers. When the linker conjugate includes unsubstituted and / or substituted ethers, the linker conjugate has the following structure: [ka] Contains one of the following:

[0059] The photoluminescent complexes of the present disclosure can include ring-locked BODIPY moieties, which can have the following general formula: [ka] In some embodiments, R1 and R2 can have the formula: 1~3 In some embodiments, R and R may be substituted aryl moieties, where the substituents on the aryl moieties are C 1~6 In some embodiments, R3 and R4 may be H, F, Br, or -CF3. In some embodiments, R5 and R6 may be H, a halide, such as -F, -Cl, and / or -Br, C1~ C alkyl groups, such as -CH, C 1~ It may be a C3 alkoxy, for example, -OCH3. In some embodiments, X may be a C1-C3 alkyl group, for example, -CH2-, -CH2CH2-, -CH2CH2CH2-, or a spirocycloalkane group.

[0060] In some embodiments, R 1 is H.

[0061] In some embodiments, R is C 1~3 It is alkyl.

[0062] In some embodiments, R2 is H.

[0063] In some embodiments, R2 is C 1~3 It is alkyl.

[0064] In some embodiments, R1 and R2 are H.

[0065] In some embodiments, R1 and R2 are C 1~3 It is alkyl.

[0066] In some embodiments, R is a substituted aryl moiety, e.g., phenyl, and the substituents on the aryl moiety, e.g., phenyl, are C 1~6 It may also be alkyl.

[0067] In some embodiments, R2 is a substituted aryl moiety, e.g., phenyl, and the substituents on the aryl moiety, e.g., phenyl, are C 1~6 It may also be alkyl.

[0068] In some embodiments, R and R are substituted aryl moieties, e.g., phenyl, and the substituents on the aryl moiety, e.g., phenyl, are C 1~6 It may also be alkyl.

[0069] In some embodiments, R3 is H.

[0070] In some embodiments, R3 is F.

[0071] In some embodiments, R3 is Br.

[0072] In some embodiments, R3 is -CF3.

[0073] In some embodiments, R4 is H.

[0074] In some embodiments, R4 is F.

[0075] In some embodiments, R4 is Br.

[0076] In some embodiments, R4 is -CF3.

[0077] In some embodiments, R3 and R4 are H.

[0078] In some embodiments, R3 and R4 are F.

[0079] In some embodiments, R3 and R4 are Br.

[0080] In some embodiments, R3 and R4 are -CF3.

[0081] In some embodiments, R5 is H.

[0082] In some embodiments, R5 is -F.

[0083] In some embodiments, R5 is -Cl.

[0084] In some embodiments, R5 is -Br.

[0085] In some embodiments, R5 is a C1-C3 alkyl group.

[0086] In some embodiments, R5 is -CH3.

[0087] In some embodiments, R5 is C1-C3 alkoxy.

[0088] In some embodiments, R5 is -OCH3.

[0089] In some embodiments, R6 is H.

[0090] In some embodiments, R6 is -F.

[0091] In some embodiments, R6 is -Cl.

[0092] In some embodiments, R6 is -Br.

[0093] In some embodiments, R6 is a C1-C3 alkyl group.

[0094] In some embodiments, R6 is -CH3.

[0095] In some embodiments, R6 is C1-C3 alkoxy.

[0096] In some embodiments, R6 is -OCH3.

[0097] In some embodiments, R5 and R6 are H.

[0098] In some embodiments, R5 and R6 are -F.

[0099] In some embodiments, R5 and R6 are -Cl.

[0100] In some embodiments, R5 and R6 are -Br.

[0101] In some embodiments, R5 and R6 are C1-C3 alkyl groups.

[0102] In some embodiments, R5 and R6 are -CH3.

[0103] In some embodiments, R5 and R6 are C1-C3 alkoxy.

[0104] In some embodiments, R5 and R6 are -OCH3.

[0105] In some embodiments, R5 and R6 can be H, -CH3, Cl, F, or OCH3.

[0106] In some embodiments, X is a C1-C3 alkyl group.

[0107] In some embodiments, X is —CH 2 .

[0108] In some embodiments, X is —CH 2 CH 2 —.

[0109] In some embodiments, X is —CH 2 CH 2 CH 2 —.

[0110] In some embodiments, X is a spirocycloalkane group.

[0111] In some embodiments, L is an unsubstituted ester.

[0112] In some embodiments, L is a substituted ester.

[0113] In some embodiments, L is an unsubstituted ether.

[0114] In some embodiments, L is a substituted ether.

[0115] Many embodiments include a blue light absorbing naphthalimide derivative (Z), which has the following general formula: [ka] wherein Y may be oxygen (O) or sulfur (S). In some embodiments, R7 and / or R8 may be hydrogen (H), substituted or unsubstituted aryl, or -CF3. In some embodiments, R9 may be H, substituted or unsubstituted aryl, C 1~5 It may be alkylaryl, substituted or unsubstituted arylcarboxylic acid (such as p-CO2-t-Bu-phenyl), or there is no substitution at R9.

[0116] In some embodiments, Y is oxygen (O).

[0117] In some embodiments, Y is sulfur (S).

[0118] In some embodiments, R7 is H.

[0119] In some embodiments, R7 is substituted aryl.

[0120] In some embodiments, R7 is unsubstituted aryl.

[0121] In some embodiments, R7 is -CF3.

[0122] In some embodiments, R8 is H.

[0123] In some embodiments, R8 is substituted aryl.

[0124] In some embodiments, R8 is unsubstituted aryl.

[0125] In some embodiments, R8 is -CF3.

[0126] In some embodiments, R7 and R8 are H.

[0127] In some embodiments, R7 and R8 are substituted aryl.

[0128] In some embodiments, R7 and R8 are unsubstituted aryl.

[0129] In some embodiments, R7 and R8 are -CF3.

[0130] In some embodiments, R9 is H.

[0131] In some embodiments, R9 is substituted aryl.

[0132] In some embodiments, R9 is unsubstituted aryl.

[0133] In some embodiments, R9 is C 1~5 It is alkylaryl.

[0134] In some embodiments, R9 is a substituted arylcarboxylic acid.

[0135] In some embodiments, R9 is an unsubstituted arylcarboxylic acid.

[0136] In some embodiments, R9 is p-CO2-t-Bu-phenyl.

[0137] Photoluminescent complexes of the present disclosure can be represented by the following structure, which is provided for illustrative purposes only and should not be construed as limiting in any way: [ka]

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[0138] In some embodiments, the photoluminescent complex includes a blue-light-absorbing naphthalimide derivative. In some examples, the blue-light-absorbing naphthalimide derivative can include an organic luminophore. In many embodiments, the blue-light-absorbing moiety can have a peak absorption maximum between about 400 nm and about 480 nm. In some embodiments, the peak absorption can be at least about 400 nm, 410 nm, 420 nm, 430 nm, 440 nm, 450 nm, or 460 nm. In some embodiments, the peak absorption can be less than about 410 nm, 420 nm, 430 nm, 440 nm, 450 nm, or 460 nm. In many embodiments, the photoluminescent complex can have an absorption maximum peak of about 450 nm. In some embodiments, the blue-light-absorbing naphthalimide derivative can have a maximum peak absorbance of about 410 nm and a minimum maximum absorption peak of about 400 nm. Additionally, in many embodiments, the blue light absorbing naphthalimide derivatives may have a maximum peak absorbance of about 480 nm.

[0139] Some embodiments include a color conversion film, which includes a color conversion layer including a resin matrix and a photoluminescent complex as described above dispersed within the resin matrix. In many embodiments, the color conversion film can include one or more photoluminescent complexes as described herein.

[0140] Some embodiments include color conversion films that can be from about 1 μm to about 200 μm thick. In many embodiments, the color conversion film can be described as being from about 1 μm to about 5 μm thick, from about 5 μm to about 10 μm thick, from about 10 μm to about 15 μm thick, from about 15 μm to about 20 μm thick, from about 20 μm to about 40 μm thick, from about 40 μm to about 80 μm thick, from about 80 μm to about 120 μm thick, from about 120 μm to about 160 μm thick, from about 160 μm to about 200 μm thick, or any thickness bounded by the above ranges.

[0141] In some embodiments, the color conversion film can absorb light in the wavelength range of about 400 nm to about 480 nm and emit light in the range of about 590 nm to about 660 nm.

[0142] In some embodiments, the color conversion film may further include a transparent substrate layer. The transparent substrate layer has two opposing surfaces, and the color conversion layer may be disposed on the surface of the transparent layer adjacent to the light source and be in physical contact with it. The transparent substrate is not particularly limited, and a person skilled in the art would 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 polyglycolic acid), PLA (polylactic acid), PCL (polycaprolactone), PEA (polyethylene adipate), PHA (polyhydroxyalkanoate), PHBV (poly(3-hydroxybutyrate-co-3-hydroxyvalerate)), PBE (polybutylene terephthalate), and PTT (polytrimethylene terephthalate). Any of the aforementioned resins may be the corresponding respective monomers and / or polymers.

[0143] In some embodiments, the transparent substrate may have two opposing surfaces. In many embodiments, the color conversion film may be disposed on one of the opposing surfaces and be in physical contact with it. In some embodiments, the surface of the transparent substrate on which the color conversion film is not disposed may be adjacent to the light source. The substrate may function as a support during the preparation of the color conversion film material. 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. Those skilled in the art will be able to determine which material and thickness should be used as the support substrate.

[0144] Some embodiments include a method of making a color conversion film, the method comprising dissolving a photoluminescent complex described herein and a binder resin in a solvent and applying the mixture to the surface of a transparent substrate.

[0145] 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 resins, polyester resins, vinyl chloride-vinyl acetate copolymer resins, polyvinyl butyral resins, polyvinyl phosphonic acid (PVPA), polystyrene resins, phenolic resins, phenoxy resins, polysulfone, nylon, cellulose resins, and cellulose acetate resins, etc. In some embodiments, the binder resin can be a polyester resin and / or an acrylic resin.

[0146] Solvents that can 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™, Butyl Cellosolve™, Methyl Cellosolve™ acetate, and Ethyl Cellosolve™. Cellosolve™ acetate, propylene glycol and its derivatives such as propylene glycol monomethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, and dipropylene glycol dimethyl ether, ketones such as acetone, methyl amyl ketone, cyclohexanone, and acetophenone, ethers such as dioxane and tetrahydrofuran, esters such as butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, diethyl oxalate, ethyl pyruvate, ethyl 2-hydroxybutyrate, ethyl acetoacetate, methyl lactate, ethyl lactate, and methyl 3-methoxypropionate, halogenated hydrocarbons such as chloroform, methyl chloride, and tetrachloroethane, aromatic hydrocarbons such as benzene, toluene, xylene, and cresol, and highly polar solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone may be mentioned.

[0147] Some embodiments include a backlight unit, which in some examples may comprise the aforementioned color conversion film containing the photoluminescent complex(es) described herein.

[0148] Other embodiments may include a display device, which may include a backlight unit as described herein.

[0149] Unless otherwise indicated, all numbers expressing properties such as amounts of ingredients, molecular weights, reaction conditions, and the like used in the specification and embodiments should be understood to be modified in all instances by the term "about." Accordingly, unless indicated to the contrary, the numerical parameters set forth in the specification and accompanying embodiments are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, and not as an attempt to limit the application of the doctrine of equivalents, within the scope of the embodiments, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0150] 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. Furthermore, the outlined steps and operations are presented by way of example only, and some steps and operations may be optional, combined into fewer steps and operations, or expanded into additional steps and operations.

[0151] This disclosure may at times describe different components contained within or associated with other different components. Such depicted configurations are merely exemplary, and many other configurations may be implemented to achieve the same or similar functionality.

[0152] Generally, the terms used in this disclosure and the accompanying embodiments (e.g., the body of the accompanying embodiments) are intended as "open" terms (e.g., the term "including" should be interpreted as "including, but not limited to," the term "having" should be interpreted as "having at least," and the term "includes" should be interpreted as "includes, but not limited to"). "to")," etc.; further, when a specific number of elements is introduced, this may be interpreted to mean at least the recited number, as may be indicated by context (e.g., the bare recitation of "two descriptions," without other modifiers, means at least two descriptions or more than two descriptions). As used in this disclosure, any disjunctive word and / or disjunctive phrase expressing two or more alternative terms should be understood to contemplate the possibility of including one of the terms, either of the terms, or both terms. For example, the phrase "A or B" will be understood to include the possibilities of "A" or "B" or "A and B." Similarly, the phrase "A and / or B" will be understood to include the possibilities of "A" or "B" or "A and B."

[0153] The terms "a," "an," "the," and similar referents used in the context of describing this disclosure (particularly in the context of the embodiments below) should be construed to cover both the singular and the plural unless otherwise indicated herein or clearly contradicted by context. The use of any and all examples or representative language (e.g., "such as" or "for instance") presented herein is intended merely to better illustrate the disclosure and does not pose a limitation on the scope of any embodiment. No language in the specification should be construed as indicating any non-embodied element essential to the practice of the disclosure.

[0154] Groupings of alternative elements or embodiments disclosed herein are not to be construed as limiting. Each group member may be referenced and embodied individually or in any combination with other members of the group or other elements found herein. It is anticipated that one or more members of a group may be included in, or deleted from, a group for reasons of convenience and / or patentability. When such inclusions or deletions are made, the specification is deemed to satisfy the description of all Markush groups used in the appended embodiments to include the modified group.

[0155] Certain embodiments are described herein, including the best mode known to the inventors for carrying out the present disclosure. Of course, variations on these described embodiments will become apparent to those skilled in the art upon reading the foregoing description. The inventors anticipate that those skilled in the art will employ such variations as appropriate, and the inventors intend for the present disclosure to be practiced otherwise than as specifically described herein. Accordingly, embodiments are as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is contemplated unless otherwise indicated herein or otherwise clearly contradicted by context. Finally, it should be understood that the embodiments disclosed herein are illustrative of the principles of the embodiments. Thus, by way of example, but not limitation, alternative embodiments can be utilized in accordance with the teachings herein. Accordingly, the embodiments are not limited to those precisely shown and described herein.

[0156] Embodiment Embodiment 1. A photoluminescent complex comprising: a blue-light absorbing donor chromophore comprising a naphthalimide derivative; a linker complex; a ring-locked boron dipyrromethene (BODIPY) moiety; Including, a photoluminescent complex, wherein the linker conjugate covalently bonds the donor chromophore having the naphthalimide derivative to the ring-locked BODIPY moiety, the naphthalimide derivative absorbs blue light energy at a first excitation wavelength and transfers the energy to the ring-locked BODIPY moiety, the ring-locked BODIPY moiety absorbs the energy from the naphthalimide derivative and emits light energy at a second, higher wavelength, and the photoluminescent complex has an emission quantum yield of greater than 80%.

[0157] Embodiment 2. The naphthalimide derivative of the donor chromophore has the general formula: [ka] 10. The photoluminescent complex of embodiment 1, wherein Y is selected from oxygen (O) or sulfur (S); R7 and R8 are independently selected from hydrogen (H), substituted or unsubstituted aryl, or —CF3; and R9 is independently selected from hydrogen (H), substituted or unsubstituted aryl, C1-C5 alkyl, or there is no substitution on R9.

[0158] Embodiment 3. The ring-locked BODIPY moiety has the general formula: [ka] wherein R1 and R2 are independently selected from H or C1-C3 alkyl; R3 and R4 are independently selected from H, F, Br, -CF3, or a bond connecting to LZ; R5 and R6 are independently selected from H, a C1-C3 alkyl group, a halide, or a C1-C3 alkoxy; and X is independently selected from a C1-C3 alkyl group, -CH2CH2-, -CH2CH2CH2-, or a spiro-cycloalkane group.

[0159] Embodiment 4. 4. The photoluminescent complex of embodiment 3, wherein L is a linker conjugate that can be a substituted ester, an unsubstituted ester, a substituted ether, or an unsubstituted ether.

[0160] Embodiment 5. 4. The photoluminescent complex of embodiment 3, wherein Z is a donor chromophore comprising the naphthalimide derivative.

[0161] Embodiment 6. The linker conjugate is an unsubstituted ester, the unsubstituted ester having the following structure: [ka] 5. The photoluminescent complex of embodiment 1 or 4, comprising one of:

[0162] Embodiment 7. The linker conjugate is a substituted ester, the substituted ester having the following structure: [ka] 5. The photoluminescent complex of embodiment 1 or 4, comprising one of:

[0163] Embodiment 8. The linker conjugate is an unsubstituted and / or substituted ether, and the unsubstituted and / or substituted ether has the following structure: [ka] 5. The photoluminescent complex of embodiment 1 or 4, comprising one of:

[0164] Embodiment 9. The photoluminescent complex has the following structure: [ka] [ka]

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[0165] Embodiment 10. A color conversion film, A transparent substrate layer; a color conversion layer including a resin matrix; At least one photoluminescent complex comprising the photoluminescent complex of embodiment 1, 2, 3, 4, 5, 6, 7, 8 or 9 dispersed within the resin matrix; and Including color conversion film.

[0166] Embodiment 11. 11. The color conversion film of embodiment 10, further comprising a singlet oxygen quencher.

[0167] Embodiment 12. 11. The color converting film of embodiment 10, further comprising a free radical scavenger.

[0168] Embodiment 13. 11. The color conversion film of embodiment 10, wherein the film has a thickness between 10 μm and 200 μm.

[0169] Embodiment 14. 11. The color conversion film of embodiment 10, wherein the film absorbs light in the wavelength range of about 400 nm to about 480 nm and emits light in the wavelength range of about 590 nm to about 650 nm.

[0170] Embodiment 15. 15. A method of making the color conversion film of embodiment 10, 11, 12, 13, or 14, comprising: Dissolving the photoluminescent complex of embodiment 1, 2, 3, 4, 5, 6, 7, 8, or 9 and a binder resin in a solvent; applying the mixture to one of the opposing surfaces of a transparent substrate; A method comprising:

[0171] Embodiment 16. A backlight unit comprising the color conversion film according to embodiment 10, 11, 12, 13, or 14.

[0172] Embodiment 17. A display device comprising a backlight unit according to embodiment 16. [Example]

[0173] It has been discovered that embodiments of the photoluminescent complexes 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 intended to illustrate the disclosure and are not intended to limit the scope or underlying principles.

[0174] The following examples are synthetic procedures for many embodiments of the naphthalimide derivatives (i.e., blue absorber intermediates) described herein.

[0175] Example 1 (Ex-1): [ka]

[0176] Ex-1.1: A mixture of 2-nitrophenol (6.6 g, 48 mmol) and KOH powder (2.4 g, 43 mmol) was mixed and stirred under vacuum for 30 minutes, then copper powder (0.4 g) was added, followed by 100 mL of anhydrous DMF. The mixture was stirred for 5 minutes, 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 then allowed 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 1 hour and then cooling to room temperature. Filtration and air drying gave a yellow solid (3.0 g, 41% yield). LCMS (APCI) analysis confirmed: C 18 H 10 Calculated for NO6 (M+H): 336.0; Found: 336. 1 H 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).

[0177] Ex-1.2: 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 to reflux for 30 minutes. The resulting solution was poured into water (220 mL). The resulting precipitate was collected by filtration, washed with water, dried thoroughly in air, and then placed under vacuum to give a yellow solid (1.65 g, 90% yield). Confirmed by LCMS (APCI): C 18 H 12 Calculated for NO4 (M+H): 306.1; Found: 306.

[0178] Ex-1.3: 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-cooled 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 °C. The whole was stirred at 0 °C for 1 hour, then transferred to an addition funnel and added dropwise to a 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 acetone, and then dried in air and then in vacuo to give a yellow solid (0.92 g, 65% yield). Confirmed by LCMS (APCI): C 18 Calculated for H8O4 (M-): 288.0; Found: 288. 1 H NMR(400MHz,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).

[0179] Ex-1: A mixture of 1H,3H-isochromeno[6,5,4-mna]xanthene-1,3-dione (100 mg, 0.347 mmol) and 2-(4-aminophenyl)acetic acid (135 mg, 0.9 mmol) in 5 mL of DMF was heated in a microwave reactor at 165 °C for 2 h. 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, washed with acetone, and dried in air to give a yellow solid (88 mg, 61% yield). LCMS (APCI) confirmed: C 26 H 15 Calculated for NO5 (M-): 421.1; Found: 421. 1 H NMR (400MHz, DMSO-d6) δ 8.27 (d, J=45.1Hz, 4H), 7.67~7.00 (m, 8H), 3.58 (s, 2H).

[0180] Example 2 (Ex-2): [ka]

[0181] Ex-2: A mixture of 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 h. 15 mL of acetone was added to the mixture, and the resulting precipitate was collected by filtration, dried in air, and then dried in a vacuum oven at 100 °C for 1 h to give a yellow solid (120 mg, 77% yield). LCMS (APCI) confirmed: C 28 H 19 Calculated for NO5 (M-): 449.1; Found: 449. 1 H NMR(400MHz,DMSO-d6) δ 8.38(d,J=41.6Hz,4H), 7.81~6.97(m,8H), 2.69~2.64(m,2H), 2.26(t,J=7.2Hz,2H), 1.87(p,J=7.2Hz,2H).

[0182] Example 3 (Ex-3): [ka]

[0183] Ex-3.1: To a mixture of compound Ex-1.3 (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 give 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% to 100% dichloromethane). The desired fractions were collected and the solvent was removed to give 110 mg of a yellow solid. A total of 400 mg of product was obtained in 89.7% yield. LCMS (APCI-): C18 Calculated for H6Br2O4: 443.9; found 444. 1 H 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).

[0184] Ex-3.2: A mixture of compound Ex-3.1 (190 mg, 0.426 mmol), 4-(4-aminophenyl)butanoic acid (180 mg, 0.64 mmol), and 4-(N,N-dimethylamino)-pyridine (4 mg) in anhydrous N,N-dimethylformamide (DMF) (4 mL) was heated at 165° C. for 2.5 hours. After the mixture was cooled to room temperature and allowed to stand overnight, the solid was collected by filtration, washed with acetone, and dried in a vacuum oven at 90° C. for 1 hour to give a yellow solid (220 mg, 84.5% yield). LCMS (APCI-): C 28 H 17 Calculated for Br2NO5: 604.95; Found: 605. 1 H NMR(400MHz,DMSO-d6) δ 9.42(dd,J=8.6,1.5Hz,1H), 8.57(d,J=4.6Hz,2H), 7.83~7.68(m,1H), 7.63~7.44(m,2H), 7.34(d,J= 8.3Hz,2H), 7.31~7.16(m,2H), 2.67(dd,J=4.8,2.8Hz,2H), 2.28(t,J=7.4Hz,2H), 1.95~1.80(m,2H).

[0185] Ex-3: A mixture of compound Ex-3.2 (100 mg, 0.165 mmol), (3,5-bis(trifluoromethyl)phenyl)boronic acid (170 mg, 0.66 mmol), Pd(dppf)Cl (20 mg, 0.027 mmol), and potassium carbonate (138 mg, 1 mmol) in THF / water (5 mL / 0.5 mL) was degassed and then heated at 80 °C for 2 h. 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 h. A yellow solid (142 mg, 94% yield) was obtained. LCMS (APCI-): C 44 H 23 F 12 Calculated for NO5: 873.14; Found: 873. 1 H 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=6.3Hz,2H), 2.72(t,J=7.6Hz,2H), 2.38(t,J=7.4Hz,2H), 2.03~1.93(m,2H).

[0186] Example 4 (Ex-4): [ka]

[0187] Ex-4.1: A mixture of 4-bromo-1,8-naphthalic anhydride (2.77 g, 10 mmol) and 4-bromo-2-nitrophenol (3.27 g, 15 mmol) was degassed under vacuum for 30 minutes, then anhydrous NMP (50 mL) was added, followed by 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 the mixture was cooled to room temperature, 50 mL of 20% aqueous hydrochloric acid was added dropwise to the solution, followed by 50 mL of water. The resulting mixture was allowed to stand for 3 hours, then filtered to collect the precipitate, which was dried under vacuum to give 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+): C 18 Calculated for H9BrNO6 (M+H) = 413.95; found: 414. 1 H NMR(400MHz,TCE-d2) δ 8.70(dd,J=8.4,1.2Hz,1H), 8.63(dd,J=7.3,1.2Hz,1H), 8.41(d,J=8.3Hz,1H), 8.2 4(d,J=2.4Hz,1H), 7.89~7.79(m,2H), 7.20(d,J=8.7Hz,1H), 6.82(d,J=8.3Hz,1H).

[0188] Ex-4.2: A mixture of compound Ex-4.1 (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 under vacuum to give a solid (1.35 g, 82% yield). LCMS (APCI-): C 18 H 10 Calculated for BrNO4 = 382.98; Found: 383. 1 H 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).

[0189] Ex-4.3: Compound Ex-4.2 (2.65 g, 6.9 mmol) was dispersed in acetic acid (50 mL) / water (10 mL) and cooled to 0° C. While stirring, pre-cooled hydrochloric acid (2.8 mL, 34.5 mmol) was added, followed by dropwise addition of a solution of sodium nitrite (3.57 g, 52 mmol) in 15 mL of water at 0° C. The whole was stirred at 0° C. for 1 hour, then transferred to an addition funnel and added dropwise to a copper sulfate solution (12 g, 47 mmol, in 140 mL of water) at 130° C. over 1 hour. After cooling to room temperature, the precipitate was collected by filtration, washed with water (100 mL×3), and then stirred in 50 mL of acetone at 40° C. for 30 minutes. Filtration, drying in air and then under vacuum gave a tan solid (1.76 g, 70% yield). LCMS (APCI+): C 18 Calculated for H8BrO4 (M+H) = 366.95; found: 367. 1 H 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).

[0190] Ex-4.4: A mixture of compound Ex-4.3 (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 heated in a microwave reactor at 165 °C for 2.5 hours. The resulting solution was added dropwise to 50 mL of acetone with stirring. The formed precipitate was filtered and dried overnight in a vacuum oven at 60 °C to give the desired product as a tan solid (0.49 g, 62% yield). LCMS (APCI-): C 28 H 18 Calculated for BrNO5 = 527.04; Found: 527. 1H NMR(400MHz,DMSO-d6) δ 8.54(d,J=2.3Hz,1H), 8.41(dd,J=9.9,8.0Hz,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), 1.87~1.73(m,2H).

[0191] Ex-4: A mixture of compound Ex-4.4 (385 mg, 0.729 mmol), phenylboronic acid (178 mg, 1.45 mmol), Pd(dppf)Cl (36 mg, 0.05 mmol), and potassium carbonate (276 mg, 2 mmol) in a cosolvent of THF / DMF / water (20 L / 4 mL / 2 mL) was degassed and then heated at 80 °C overnight. The mixture was worked up with 200 mL of ethyl acetate and 50 mL of 0.6 N aqueous hydrochloric acid. The aqueous phase was extracted with ethyl acetate (100 mL × 2). The organic phase was collected, washed with brine (100 mL × 2), dried over sodium sulfate, and then dry loaded onto silica gel and purified by flash chromatography using an eluent of DCM / EA (0% → 40% EA with 0.1% TFA). The main desired fraction was collected and the solvent removed under reduced pressure to give a yellow solid (250 mg, 65% yield). LCMS (APCI-): C 34 H 23 Calculated for NO5 = 525.16; Found: 525. 1 H 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=7.3 Hz,2H), 7.51~7.28(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).

[0192] Example 5 (Ex-5) [ka]

[0193] Ex-5: A mixture of compound Ex-4.4 (385 mg, 0.729 mmol), 3,5-bis-(trifluoromethyl)phenylboronic acid (374 mg, 1.45 mmol), Pd(dppf)Cl (36 mg, 0.05 mmol), and potassium carbonate (276 mg, 2 mmol) in a cosolvent of THF / DMF / water (20 L / 4 mL / 2 mL) was degassed and then heated at 80 °C overnight. The mixture was worked up with 200 mL of ethyl acetate and 50 mL of 0.6 N aqueous hydrochloric acid. The aqueous phase was extracted with ethyl acetate (100 mL × 2). The organic phase was collected, washed with brine (100 mL × 2), dried over sodium sulfate, and then dry-loaded onto silica gel and purified by flash chromatography using an eluent of DCM / EA (0% → 40% EA containing 0.1% TFA). The main desired fraction was collected and the solvent removed under reduced pressure to give a yellow solid (340 mg, 70.5% yield). LCMS (APCI-): C 36 H 21 Calculated for F6NO5 = 661.13; Found: 661. 1 H 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), 8.03~7.98(m,2H), 7.87(s,1H), 7.72(dd,J=8.6,2.2Hz,1 H), 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).

[0194] Example 6 (Ex-6) [ka]

[0195] Ex-6: A mixture of 1H,3H-thioxantheno[2,1,9-def]isochromene-1,3-dione (458 mg, 1.5 mmol), 4-(4-aminophenyl)butanoic acid (537 mg, 3 mmol), and DMAP (14 mg, 0.11 mmol) in 10 mL of DMF was heated in a microwave reactor at 165 °C for 2.5 h. The resulting solution was added dropwise to 60 mL of acetone with stirring. An orange precipitate formed, which was filtered, washed with diethyl ether, and dried in air to give an orange solid (546 mg), which was dried in a vacuum oven at 100 °C for 3 h to give the desired product as an orange solid (500 mg, 71.7% yield). Confirmed by LCMS (APCI-): C 28 H 19 Calculated for NO4S = 465.10; Found: 465. 1 H 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), 7.65~7.58(m,1H), 7.52(tt,J=7. 2,5.5Hz,2H), 7.37~7.30(m,2H), 7.30~7.23(m,2H), 2.69(t,J=7.4Hz,2H), 2.29(t,J=7.3Hz,2H), 1.88(p,J=7.5Hz,2H).

[0196] The following examples are synthetic procedures for many embodiments of the pyrrole intermediates described herein.

[0197] Example 7 (Ex-7.3): [ka]

[0198] Ex-7.2 - General procedure for the synthesis of compound Ex-7.2, (E)-6,7,8,9-tetrahydro-5H-benzo[7]annulen-5-one oxime: A mixture of compound Ex-7.1 (10.0 g, 62.0 mmol), NHOH·HCl (6.50 g, 93.0 mmol), and NaOAc (12.7 g, 155.0 mmol) in EtOH / HO (45 mL / 150 mL) was placed in a 500 mL two-neck round-bottom flask equipped with a reflux condenser. The solution was heated to reflux at 115 °C and held at this temperature for 1 h. TLC (50% EtOAc in hexanes) indicated the reaction was complete. After cooling to 0 °C and filtration, compound Ex-7.2 was obtained as a pale white solid (quantitative yield) for the next step without further purification. MS (APCI): C 11 H 14 Calculated value for NO ([M+H] + )=176 Actual value: 176. 1 H NMR(400MHz,CDCl3) δ 7.98(bs,1H), 7.39(dd,J=7.6Hz,1.6Hz,1H), 7.30(td,J=7.6Hz,1.6Hz,1H), 7.23(td,J=7.6Hz,1.6Hz,1H), 7.13 (d,J=7.6Hz,1H), 2.74(m,4H), 1.78(ddd,J=13.2Hz,6.0Hz,6.0Hz,2H), 1.65(ddd,J=12.4Hz,6.0Hz,6.0Hz,2H).

[0199] General procedure for the synthesis of Ex-7.3—Compound Ex-7.3, 1,4,5,6-tetrahydrobenzo[6,7]cyclohepta[1,2-b]pyrrole: A solution of compound Ex-7.2 (8.8 g, 50.0 mmol) and KOH (10.1 g, 180.0 mmol) in DMSO (50 mL) was placed in a 250 mL two-neck round-bottom flask equipped with a reflux condenser. The solution was degassed at room temperature and heated to 140 °C. To this solution, a separate solution of DCE (12.4 g, 125 mmol) in DMSO (50 mL) was added dropwise via syringe pump over 5.5 h. After the addition of the DCE solution was complete, the reaction was cooled to room temperature and then poured into saturated NH4Cl solution (500 mL). The desired product was extracted from the workup solution using EtOAc (500 mL × 3). The combined organic layers were dried over anhydrous NaSO, concentrated in vacuo, and purified by silica gel flash chromatography using DCM in hexanes (0→30%) as the eluent to give compound Ex-7.3 as a pale white solid (4.6 g, 50% yield). MS (APCI): C 13 H 14 Calculated values ​​for N ([M+H] + )=184 Actual value: 184. 1 H NMR(400MHz,CDCl3) δ 8.19(bs,1H), 7.34(dd,J=8.0Hz,1.6Hz,1H), 7.22(td,J=7.6Hz,1.6Hz,1H), 7.16(dd,J=7.6Hz,1.6Hz,1H), 7.09(td ,J=7.6Hz,1.6Hz,1H), 6.84(t,J=2.8Hz,1H), 6.16(t,J=2.8Hz,1H), 2.90(t,J=6.8Hz,2H), 2.83(m,2H), 2.02(m,2H).

[0200] Example 8 (Ex-8.2): [ka]

[0201] General procedure for the synthesis of compound Ex-8.2, 4,5-dihydro-1H-benzo[g]indole: A mixture of NHOH·HCl (4.2 g, 60.0 mmol) and KOH (3.4 g, 60.0 mmol) in DMSO (50 mL) was placed in a 500 mL two-neck round-bottom flask equipped with a reflux condenser. The solution was stirred at room temperature for 30 min. Compound Ex-8.1 (7.3 g, 50.0 mmol) in DMSO (25 mL) was then added. The solution was heated to 70 °C and maintained at this temperature for 30 min. Another portion of KOH (8.4 g, 150.0 mmol) was then added to the solution, followed by heating the solution to 140 °C. To this solution, another solution of DCE (9.9 g, 100.0 mmol) in DMSO (25 mL) was added dropwise over 4 h via syringe pump. After the addition of the DCE solution was completed, the reaction was cooled to room temperature and then poured into saturated NH4Cl solution (200 mL). EtOAc (200 mL x 3) was used to extract the desired product from the work-up solution. The combined organic layer was dried over anhydrous Na2SO4, concentrated under vacuum, and purified by silica gel flash chromatography using DCM in hexane (0->30%) as the eluent to give compound Ex-8.2 as a pale white solid (3.7 g, 43% yield). MS (APCI): C 12 H 12 Calculated values ​​for N ([M+H] + )=170 Actual value: 170. 1 H NMR(400MHz,CDCl3) δ 8.28(bs,1H), 7.22(ddd,J=17.6Hz,10.4Hz,10.4Hz,2H), 7.16(t,J=7.2Hz,1H), 7.08(td, J=7.2,1.6Hz,1H), 6.76(m,1H), 6.15(m,1H), 2.96(t,J=7.2Hz,2H), 2.78(t,J=7.2Hz,2H).

[0202] Example 9 - Synthesis of Photoluminescent Complex (PLC): The following examples provide synthetic procedures for many embodiments of the RL-naphthalimide-BODIPYs described herein.

[0203] Synthesis of PLC-1: [ka]

[0204] General procedure for compound PLC-1.3: A 100 mL two-neck round-bottom flask was equipped with an air condenser and a stir bar. Compounds 1,4,5,6-tetrahydrobenzo[6,7]cyclohepta[1,2-b]pyrrole PLC-1.1 (813.1 mg, 4.4 mmol) and 4-hydroxy-2,6-dichlorobenzaldehyde PLC-1.2 (424.3 mg, 2.2 mmol) were added to the flask, followed by anhydrous dichloroethane (55 mL). The reaction mixture was sparged with Ar for 30 minutes, and then TFA (4 drops) was added. The reaction solution was stirred overnight at room temperature. The reaction was cooled to 0 °C in an ice-water bath, followed by the addition of p-chloranil (731.8 mg, 2.98 mmol). The reaction was held at 0 °C for 30 minutes. Then, BF3·OEt2 (3.0 mL, 24.1 mmol) and Et3N (1.9 mL, 13.3 mmol) were added at 0 °C. The reaction mixture was heated to 50 °C for 3 h. The reaction mixture was loaded onto silica gel and purified by flash chromatography using DCM in hexanes (0% → 80% → 90%) as the eluent to give pure BODIPY PLC-1.3 as a golden brown solid (476.0 mg, 36% yield). MS (APCI): C 33 H 24 Calculated value for BCl2F2N2O ([MH] - )=584 Actual value: 584. 1 H NMR(400MHz, CDCl3) 8.09(dd,J=4.0Hz,2.0Hz,2H), 7.32(dddd,J=13.2Hz,7.2Hz,7.2Hz,2.0Hz,4H), 7.22(dd,J=6.4Hz,2.0Hz,2H), 6.99(s ,2H), 6.43(s,2H), 5.77(bs,1H), 2.63(dd,J=6.8Hz,6.8Hz,4H), 2.32(bs,4H), 2.03(ddd,J=14.0Hz,6.8Hz,6.8Hz,4H).

[0205] General procedure for compound PLC-1: A 10 mL vial was equipped with a stir bar. Compounds PLC-1.3 (25.0 mg, 0.043 mmol), PLC-1.4 (24.0 mg, 0.053 mmol), EDC·HCl (40.9 mg, 0.21 mmol), and DMAP·TsOH (25.6 mg, 0.085 mmol) were added to the vial, followed by anhydrous DCM (1.5 mL). The reaction mixture was heated to 40 °C overnight. After the reaction cooled to room temperature, the reaction mixture was loaded onto silica gel and purified by flash chromatography using DCM in EtOAc (0% to 5%) as the eluent to afford pure RL-naphthalimide-BODIPY PLC-1 as a dark purple solid. The solid was further triturated with MeOH (10 mL) to afford RL-naphthalimide-BODIPY PLC-1 (21.0 mg, 48% yield). MS (APCI): C 61 H 41 Calculated value for Cl2F2N3O5 ([MH] - )=1015 Actual value: 1015. 1 H NMR(400MHz,CDCl3) 8.66(dd,J=18.4Hz,7.6Hz,2H), 8.10(m,3H), 7.99(d,J =8.0Hz,1H), 7.56(ddd,J=8.0Hz,8.0Hz,1.6Hz,1H), 7.36(m,13H), 7.22(dd,J=6.8Hz,2.0Hz,2H), 6.45(s,2H) 2.88(t,J=7.6Hz,2H), 2.72(t,J=7.2Hz,2H), 2.63(m,4H), 2.20(m,6H), 2.04(ddd,J=6.8Hz,6.8Hz,6.8Hz,4H).

[0206] Synthesis of PLC-2: [ka]

[0207] General procedure for compound PLC-2: A mixture of compound PLC-2.1 (31 mg, 0.053 mmol), compound PLC-2.2 (43 mg, 0.082 mmol), EDC·HCl (100 mg, 0.52 mmol), and DMAP / p-TsOH (16 mg, 0.054 mmol) in DCM (8 mL) was stirred overnight at room temperature. The resulting mixture was then loaded onto silica gel and purified by flash chromatography using an eluent of DCM / ethyl acetate (0% to 5% ethyl acetate). The main red fraction was collected and concentrated under reduced pressure to approximately 1 mL, followed by the addition of 10 mL of methanol. The resulting precipitate was filtered and dried in air to give a dark red solid (41 mg, 70.8% yield). LCMS (APCI-): C 67 H 46 Calculated for BCl2F2N3O5 (M-) = 1091.29; Found: 1091. 1 H NMR(400MHz,d2-TCE) δ 8.56(dd,J=19.3,8.1Hz,2H), 8.21(d,J=2.2Hz,1H), 8.02(d,J=8.1Hz,1H), 7.97(t,J=4.7Hz ,2H), 7.73(dd,J=8.6,2.1Hz,1H), 7.63(dd,J=7.2,1.7Hz,2H), 7.50~7.41(m,3H), 7.38(dd,J =8.0,2.2Hz,3H), 7.34~7.25(m,7H), 7.25~7.18(m,4H), 6.40(s,2H), 2.82(t,J=7.5Hz,2H), 2.67(t,J=7.4Hz,2H), 2.60~2.49(m,4H), 2.24(s,4H), 2.18~2.07(m,2H), 2.03~1.90(m,4H).

[0208] Synthesis of PLC-3: [ka]

[0209] General procedure for compound PLC-3: A mixture of compound PLC-3.1 (28 mg, 0.048 mmol), compound PLC-2.1 (70 mg, 0.08 mmol), DIC (0.1 mL, 0.63 mmol), and DMAP / TsOH salt (29 mg, 0.1 mmol) in anhydrous dichloromethane (5 mL) was stirred at room temperature for 40 hours. The resulting mixture was loaded onto silica gel and purified by flash chromatography using an eluent of hexane / dichloromethane (50% → 100% dichloromethane). The desired fractions were collected. After removal of the solvent and washing with methanol, a dark red solid was obtained after filtration and dried in air (45 mg, 65% yield). LCMS (APCI-): C 77 H 46 BCl2F 14 Calculated for N3O5 (M-) = 1439.27; Found: 1439. 1 H NMR(400MHz,d2-TCE) δ 8.66(s,1H), 8.41(s,1H), 8.18(d,J=1.5Hz,2H), 7.96(d,J=18.4Hz,6H), 7.39(dd,J=8.3,2.4Hz,3H), 7.34~7.12(m,11H), 6.98~6.85( m,2H), 6.39(s,2H), 2.82(t,J=7.6Hz,2H), 2.66(t,J=7.4Hz,2H), 2.54(d,J=6.1Hz,4H), 2.24(m,4H), 2.15~2.06(m,2H), 1.96(m,4H).

[0210] [ka] Synthesis of PLC-4:

[0211] General procedure for compound PLC-4.3: A 100 mL two-neck round-bottom flask was equipped with an air condenser and a stir bar. Compounds 4,5-dihydro-1H-benzo[g]indole PLC-4.1 (203.1 mg, 1.2 mmol) and 4-hydroxy-2,6-dimethylbenzaldehyde PLC-4.2 (90.0 mg, 0.6 mmol) were added to the flask, followed by anhydrous dichloroethane (15 mL). The reaction mixture was sparged with Ar for 30 minutes, and then TFA (3 drops) was added. The reaction solution was heated to 40°C and stirred at 40°C overnight. The reaction was cooled to 0°C in an ice-water bath, after which p-chloranil (200.0 mg, 0.8 mmol) was added. The reaction was held at 0°C for 30 minutes. Then, BF3·OEt2 (0.8 mL, 6.5 mmol) and Et3N (0.5 mL, 3.6 mmol) were added at 0 °C. The reaction mixture was heated to 50 °C for 2 h. The reaction mixture was loaded onto silica gel and purified by flash chromatography using DCM in hexanes (0% → 80% → 90%) as the eluent to give pure BODIPY PLC-4.3 as a dark purple-gold solid (242.2 mg, 78% yield). MS (APCI): C 33 H 28 Calculated for BF2N2O ([M+H] + )=517 Actual value: 517. 1 H NMR(400MHz, CDCl3) 8.80(d,J=8.0Hz,2H), 7.44(td,J=7.2Hz,1.6Hz,2H), 7.31(td,J=7.6Hz,1.2Hz,2H), 7.25(m,2H), 6.63(s,2H), 6.33(s,2H), 4.82(s,1H), 2.91(t,J=6.4Hz,4H), 2.65(t,J=6.4Hz,4H), 2.18(s,6H).

[0212] General procedure for compound PLC-4: A 10 mL vial was equipped with a stir bar. Compounds PLC-4.3 (25.0 mg, 0.048 mmol), PLC-4.4 (27.2 mg, 0.061 mmol), EDC·HCl (46.4 mg, 0.24 mmol), and DMAP·TsOH (29.0 mg, 0.097 mmol) were added to the vial, followed by anhydrous DCM (1.5 mL). The reaction mixture was heated to 40 °C overnight. After cooling to room temperature, the reaction mixture was loaded onto silica gel and purified by flash chromatography using DCM in EtOAc (0% to 5%) as the eluent to afford pure RL-naphthalimide-BODIPY PLC-4 as a blue-green solid. The solid was further triturated with MeOH (10 mL) to afford RL-naphthalimide-BODIPY PLC-4 (20.1 mg, 44% yield). MS (APCI): C 61 H 43 Calculated value for BF2N3O5 ([MH] - )=947 Actual value: 947. 1 H NMR(400MHz, CDCl3) 8.80(d,J=8.4Hz,2H), 8.66(dd,J=18.4Hz,8.0Hz,2H), 8.11(dd,J=8.0Hz,1.6Hz,1H), 7.99(d,J=8.0Hz,1H), 7.56(ddd,J=8.0H) z,8.0Hz,1.6Hz,1H), 7.37(m,11H), 7.25(m,2H), 6.93(s,2H), 6.35(s,2H), 2.90(m,6H), 2.68(m,6H), 2.24(s,6H), 2.20(m,2H).

[0213] Synthesis of PLC-5: [ka]

[0214] General procedure for compound PLC-5.3: A 100 mL two-neck round-bottom flask was equipped with an air condenser and a stir bar. Compound 4,5-dihydro-1H-benzo[g]indole PLC-5.1 (203.1 mg, 1.2 mmol) and 4-hydroxy-2,6-dichlorobenzaldehyde PLC-5.2 (114.6 mg, 0.6 mmol) were added to the flask, followed by anhydrous dichloroethane (15 mL). The reaction mixture was sparged with Ar for 30 minutes, and then TFA (3 drops) was added. The reaction solution was stirred overnight at room temperature. The reaction was cooled to 0 °C in an ice-water bath, followed by the addition of p-chloranil (200.0 mg, 0.8 mmol). The reaction was held at 0 °C for 30 minutes. BF OEt (0.8 mL, 6.5 mmol) and EtN (0.5 mL, 3.6 mmol) were then added at 0 °C. The reaction mixture was heated to 50° C. for 2 hours. The reaction mixture was loaded onto silica gel and purified by flash chromatography using DCM in hexanes (0% → 80% → 90%) as the eluent to give pure BODIPY PLC-5.3 as a dark purple-gold solid (200.3 mg, 57% yield). MS (APCI): C 31 H 20 Calculated value for BCl2F2N2O ([MH] - )=556 Actual value: 556. 1 H NMR(400MHz, CDCl3) 8.80(d,J=8.0Hz,2H), 7.44(td,J=7.6Hz,1.6Hz,2H), 7.32(td,J=7.6Hz,1.2Hz,2H), 7.25(m ,2H), 6.99(s,2H), 6.35(s,2H), 5.68(bs,1H), 2.93(t,J=7.6Hz,4H), 2.68(t,J=7.6Hz,4H).

[0215] General procedure for compound PLC-5: A 10 mL vial was equipped with a stir bar. Compounds PLC-5.3 (25.0 mg, 0.045 mmol), PLC-5.4 (25.2 mg, 0.056 mmol), EDC·HCl (43.0 mg, 0.22 mmol), and DMAP·TsOH (26.9 mg, 0.089 mmol) were added to the vial, followed by anhydrous DCM (1.5 mL). The reaction mixture was heated to 40 °C overnight. After the reaction cooled to room temperature, the reaction mixture was loaded onto silica gel and purified by flash chromatography using DCM in EtOAc (0% to 5%) as the eluent to afford pure RL-naphthalimide-BODIPY PLC-5 as a green solid. The solid was further triturated with MeOH (10 mL) to afford RL-naphthalimide-BODIPY PLC-5 (16.0 mg, 36% yield). MS (APCI): C 59 H 37 Calculated value for BCl2F2N3O5 ([MH] - )=986 Actual value: 986. 1 H NMR(400MHz, CDCl3) 8.80(d,J=8.4Hz,2H), 8.66(dd,J=18.0Hz,8.0Hz,2H), 8.11(dd,J=8.0Hz,1.6Hz,1H), 7.99(d,J=8.0Hz,1H), 7.56(ddd,J=8.0Hz,8 .0Hz,1.6Hz,1H), 7.34(m,15H), 6.37(s,2H), 2.90(m,6H), 2.70(dd,J=14.8Hz,7.6Hz,6H), 2.24(ddd,J=7.6Hz,7.6Hz,7.6Hz,2H).

[0216] Synthesis of PLC-6: [ka]

[0217] General procedure for PLC-6.3: A 100 mL two-neck round-bottom flask was equipped with an air condenser and a stir bar. Compounds 1,4,5,6-tetrahydrobenzo[6,7]cyclohepta[1,2-b]pyrrole PLC-6.1 (220.0 mg, 1.2 mmol) and 4-hydroxy-2,6-dimethyloxybenzaldehyde PLC-6.2 (109.3 mg, 0.6 mmol) were added to the flask, followed by anhydrous dichloroethane (15 mL). The reaction mixture was sparged with Ar for 30 minutes, and then TFA (3 drops) was added. The reaction solution was heated to 40 °C and stirred at 40 °C overnight. The reaction was cooled to 0 °C in an ice-water bath, after which p-chloranil (200.0 mg, 0.8 mmol) was added. The reaction was kept at 0 °C for 30 minutes. Then, BF3·OEt2 (0.8 mL, 6.5 mmol) and Et3N (0.5 mL, 3.6 mmol) were added at 0 °C. The reaction mixture was heated to 50 °C for 2 h. The reaction mixture was loaded onto silica gel and purified by flash chromatography using DCM in hexanes (0% → 80% → 90%) as the eluent to give pure BODIPY PLC-6.3 as a dark purple solid (28.0 mg, 8% yield). MS (APCI): C 35 H 30 Calculated value for BF2N2O3 ([MH] - )=576 Actual value: 576.1H NMR(400MHz,CDCl3) 8.10(d,J=7.6Hz,2H), 7.29(dddd,J=17.2Hz,7.2Hz,7.2Hz,4H), 7.21(dd,J=7.2Hz,2H), 6.48(s,2H), 6.19 (s,2H), 3.72(s,6H), 2.62(dd,J=6.8Hz,6.8Hz,4H), 2.29(bs,4H), 2.02(ddd,J=14.0Hz,7.2Hz,7.2Hz,4H).

[0218] General procedure for PLC-6: A 10 mL vial was equipped with a stir bar. Compounds PLC-6.3 (28.0 mg, 0.049 mmol), PLC-6.4 (27.3 mg, 0.061 mmol), EDC·HCl (46.6 mg, 0.24 mmol), and DMAP·TsOH (29.2 mg, 0.097 mmol) were added to the vial, followed by anhydrous DCM (1.5 mL). The reaction mixture was heated to 40 °C overnight. After cooling to room temperature, the reaction mixture was loaded onto silica gel and purified by flash chromatography using DCM in EtOAc (0% to 5%) as the eluent to afford pure RL-naphthalimide-BODIPY PLC-6 as a dark red-purple solid. The solid was further triturated with MeOH (10 mL) to afford RL-naphthalimide-BODIPY PLC-6 (4.0 mg, 8% yield). MS (APCI): C 63 H 47 Calculated value for BF2N3O7 ([MH] - )=1007 Actual value: 1007. 1 H NMR(400MHz, CDCl3) 8.66(dd,J=18.4Hz,8.0Hz,2H), 8.11(dd,J=8.0Hz,1.6Hz,3H), 7.99(d,J=8.0Hz,1H), 7.56(d dd,J=8.0Hz,8.0Hz,1.6Hz,1H), 7.41(m,4H), 7.32(m,7H), 7.21(dd,J=7.2Hz,1.6Hz,2H), 6.5 0(s,2H), 6.49(s,2H), 3.77(s,6H), 2.89(t,J=7.2Hz,2H), 2.72(t,J=7.2Hz,2H), 2.62(m,4H) , 2.30(bs,2H), 2.21(ddd,J=7.6Hz,7.6Hz,7.6Hz,4H), 2.02(ddd,J=6.8Hz,6.8Hz,6.8Hz,4H).

[0219] [ka] Synthesis of PLC-7:

[0220] General procedure for PLC-7.3: A 100 mL two-neck round-bottom flask was equipped with an air condenser and a stir bar. Compounds 4,5-dihydro-1H-benzo[g]indole PLC-7.1 (203.1 mg, 1.2 mmol) and 4-hydroxy-2,6-dimethoxybenzaldehyde PLC-7.2 (109.3 mg, 0.6 mmol) were added to the flask, followed by anhydrous dichloroethane (15 mL). The reaction mixture was sparged with Ar for 30 minutes, and then TFA (3 drops) was added. The reaction solution was heated to 40°C and stirred at 40°C overnight. The reaction was cooled to 0°C in an ice-water bath, after which p-chloranil (200.0 mg, 0.8 mmol) was added. The reaction was held at 0°C for 30 minutes. Then, BF3·OEt2 (0.8 mL, 6.5 mmol) and Et3N (0.5 mL, 3.6 mmol) were added at 0 °C. The reaction mixture was heated to 50 °C for 2 h. The reaction mixture was loaded onto silica gel and purified by flash chromatography using DCM in hexanes (0% → 80% → 90%) as the eluent to give pure BODIPY PLC-7.3 as a golden brown solid (78.4 mg, 24% yield). MS (APCI): C 33 H 28 Calculated value for BF2N2O3 ([M+H] + )=549 Actual value: 549. 1 H NMR(400MHz, CDCl3) 8.80(d,J=8.0Hz,2H), 7.43(t,J=8.0Hz,2H), 7.29(m,2H), 7.23(d,J=7.2Hz,2H), 6.41(s, 2H), 6.17(s,2H), 5.05(bs,1H), 3.69(s,6H), 2.90(t,J=6.8Hz,4H), 2.65(t,J=6.8Hz,4H).

[0221] General procedure for PLC-7: A 10 mL vial was equipped with a stir bar. Compounds PLC-7.3 (25.0 mg, 0.045 mmol), PLC-7.4 (25.6 mg, 0.057 mmol), EDC·HCl (43.7 mg, 0.23 mmol), and DMAP·TsOH (27.4 mg, 0.091 mmol) were added to the vial, followed by anhydrous DCM (1.5 mL). The reaction mixture was heated to 40 °C overnight. After the reaction cooled to room temperature, the reaction mixture was loaded onto silica gel and purified by flash chromatography using DCM in EtOAc (0% to 5%) as the eluent to afford pure RL-naphthalimide-BODIPY PLC-7 as a dark green solid. The solid was further triturated with MeOH (10 mL) to afford RL-naphthalimide-BODIPY PLC-7 (23.0 mg, 51% yield). MS (APCI): C 61 H 43 Calculated value for BF2N3O7 ([MH] - )=979 Actual value: 979. 1 H NMR(400MHz, CDCl3) 8.81(d,J=8.0Hz,2H), 8.67(dd,J=18.4Hz,7.6Hz,2H), 8.11(dd,J=8.0Hz,1.6Hz,1H), 8.00(d,J=8.0Hz,1H), 7.56(ddd,J=8.0Hz,8.0Hz,1.6Hz,1H), 7 .34(m,11H), 7.23(m,2H), 6.46(s,2H), 6.43(s,2H), 3.73(s,6H), 2.89(dd, J=14.0Hz,6.4Hz,6H), 2.68(m,6H), 2.24(ddd,J=7.6Hz,7.6Hz,7.6Hz,2H).

[0222] Synthesis of PLC-8: [ka]

[0223] General procedure for PLC-8.3: A 100 mL two-neck round-bottom flask was equipped with an air condenser and a stir bar. Compounds 1,4,5,6-tetrahydrobenzo[6,7]cyclohepta[1,2-b]pyrrole PLC-8.1 (220.0 mg, 1.2 mmol) and 4-hydroxy-2,6-dimethylbenzaldehyde PLC-8.2 (90.0 mg, 0.6 mmol) were added to the flask, followed by anhydrous dichloroethane (15 mL). The reaction mixture was sparged with Ar for 30 minutes, and then TFA (3 drops) was added. The reaction solution was heated to 40 °C overnight. The reaction was cooled to 0 °C in an ice-water bath, after which p-chloranil (200.0 mg, 0.8 mmol) was added. The reaction was held at 0 °C for 20 minutes. Then, BF3·OEt2 (0.8 mL, 6.5 mmol) and Et3N (0.5 mL, 3.6 mmol) were added at 0 °C. The reaction mixture was heated to 50 °C for 2 h. The reaction mixture was loaded onto silica gel and purified by flash chromatography using DCM in hexanes (0% → 80% → 90%) as the eluent to give pure BODIPY PLC-8.3 as a dark purple solid (162.5 mg, 48% yield). MS (APCI): C 35 H 30 Calculated value for BF2N2O ([MH] - )=543 Actual value: 543. 1 H NMR(400MHz, CDCl3) 8.08(d,J=7.2Hz,2H), 8.02(bs,1H), 7.28(m,6H), 6.66(bs,2H), 6.41(bs,2H), 2.96(bs,4H), 2.89(bs,4H), 2.62(m,4H), 2.22(s,6H).

[0224] General procedure for PLC-8: A 10 mL vial was equipped with a stir bar. Compounds PLC-8.3 (25.0 mg, 0.046 mmol), PLC-8.4 (25.8 mg, 0.057 mmol), EDC·HCl (44.1 mg, 0.23 mmol), and DMAP·TsOH (27.6 mg, 0.092 mmol) were added to the vial, followed by anhydrous DCM (1.5 mL). The reaction mixture was heated to 40 °C overnight. After cooling to room temperature, the reaction mixture was loaded onto silica gel and purified by flash chromatography using DCM in EtOAc (0% to 5%) as the eluent to afford pure RL-naphthalimide-BODIPY PLC-8 as a dark red-purple solid. The solid was further triturated with MeOH (10 mL) to afford RL-naphthalimide-BODIPY PLC-8 (31.0 mg, 69% yield). MS (APCI): C 63 H 47 Calculated value for BF2N3O5 ([MH] - )=975 Actual value: 975. 1 H NMR(400MHz, CDCl3) 8.66(dd,J=18.4Hz,7.6Hz,2H), 8.10(td,J=8.0Hz,1.6Hz,2H), 8.08(bs,1H), 7.99(d,J=8.0Hz,1H), 7.56 (ddd,J=8.0Hz,8.0Hz,1.6Hz,1H), 7.36(m,11H), 7.22(dd,J=7.2Hz,2.0Hz,2H), 6.95(s,2H), 6.43(s,2H) 2.88(t,J=7.2Hz,2H), 2.70(t,J=7.2Hz,2H), 2.62(m,4H), 2.29(s,6H), 2.20(m,6H), 2.02(ddd,J=6.8Hz,6.8Hz,6.8Hz,4H).

[0225] Synthesis of PLC-9: [ka]

[0226] General procedure for PLC-9: A 10 mL vial was equipped with a stir bar. Compounds PLC-9.1 (25.0 mg, 0.048 mmol), PLC-9.2 (27.2 mg, 0.061 mmol), EDC·HCl (46.4 mg, 0.24 mmol), and DMAP·TsOH (29.0 mg, 0.097 mmol) were added to the vial, followed by anhydrous DCM (1.5 mL). The reaction mixture was heated to 40 °C overnight. After cooling to room temperature, the reaction mixture was loaded onto silica gel and purified by flash chromatography using DCM in EtOAc (0% to 5%) as the eluent to afford pure RL-naphthalimide-BODIPY PLC-9 as a dark green solid. The solid was further triturated with MeOH (10 mL) to afford RL-naphthalimide-BODIPY PLC-9 (25.0 mg, 54% yield). MS (APCI): C 61 H 43 Calculated value for BF2N3O5 ([MH] - )=947 Actual value: 947. 1 H NMR(400MHz, CDCl3) 8.67(dd,J=18.4Hz,7.6Hz,2H), 8.10(m,3H), 7.99(d,J=8.0Hz,1H), 7.56( ddd,J=8.0Hz,8.0Hz,1.6Hz,1H), 7.34(m,11H), 7.23(m,2H), 6.95(m,2H), 2 .88(t,J=7.2Hz,2H), 2.70(t,J=7.2Hz,2H), 2.62(m,4H), 2.29(s,6H), 2.20(ddd,J=7.6Hz,7.6Hz,7.6Hz,6H), 2.24(ddd,J=7.6Hz,7.6Hz,7.6Hz,2H).

[0227] Synthesis of PLC-10: [ka]

[0228] General procedure for PLC-10: A 10 mL vial was equipped with a stir bar. Compounds PLC-10.1 (30.0 mg, 0.055 mmol), PLC-10.2 (32.1 mg, 0.069 mmol), EDC·HCl (52.7 mg, 0.275 mmol), and DMAP·TsOH (33.0 mg, 0.110 mmol) were added to the vial, followed by anhydrous DCM (1.5 mL). The reaction mixture was heated to 40 °C overnight. After cooling to room temperature, the reaction mixture was loaded onto silica gel and purified by flash chromatography using DCM in EtOAc (0% → 5%) as the eluent to afford pure RL-naphthalimide-BODIPY PLC-10 as a dark purple solid. The solid was further triturated with MeOH (10 mL) to afford RL-naphthalimide-BODIPY PLC-10 (51.0 mg, 94% yield). MS(APCI):C 63 H 48 Calculated value for BF2N3O4S ([MH] - )=991 Actual value: 991. 1 H NMR(400MHz, CDCl3) 8.68(d,J=8.0Hz,1H), 8.48(d,J=8.0Hz,1H), 8.26(m,2H), 8.09(m,2H) , 7.56(d,J=8.0Hz,1H), 7.44(m,5H), 7.32(m,6H), 7.22(m,2H), 6.95(s, 2H), 6.43(s,2H), 2.88(t,J=7.6Hz,2H), 2.70(t,J=7.6Hz,2H), 2.62(m,4H), 2.29(s,6H), 2.20(m,6H), 2.24(ddd,J=6.8Hz,6.8Hz,6.8Hz,4H).

[0229] Synthesis of PLC-11: [ka]

[0230] General procedure for PLC-11: A 10 mL vial was equipped with a stir bar. Compounds PLC-11.1 (30.0 mg, 0.058 mmol), PLC-11.2 (33.8 mg, 0.073 mmol), EDC·HCl (55.6 mg, 0.290 mmol), and DMAP·TsOH (34.8 mg, 0.116 mmol) were added to the vial, followed by anhydrous DCM (1.5 mL). The reaction mixture was heated to 40 °C overnight. After cooling to room temperature, the reaction mixture was loaded onto silica gel and purified by flash chromatography using DCM in EtOAc (0% → 5%) as the eluent to afford pure RL-naphthalimide-BODIPY PLC-11 as a dark green solid. The solid was further triturated with MeOH (10 mL) to afford RL-naphthalimide-BODIPY PLC-11 (40.0 mg, 72% yield). MS(APCI):C 61 H 44 Calculated value for BF2N3O4S ([MH] - )=963 Actual value: 963. 1 H NMR(400MHz, CDCl3) 8.81(d,J=8.0Hz,2H), 8.68(d,J=8.0Hz,1H), 8.48(d,J=8.0Hz,1H), 8.26(m,2H), 7.56(d,J=8.0Hz,1H), 7.44(m,7H), 7.29(m,6H), 6.93(s,2H), 6.35(s,2H), 2.90(m,6H), 2.68(m,6H), 2.24(s,6H), 2.19(m,2H).

[0231] Synthesis of PLC-12: [ka]

[0232] General procedure for PLC-12: A 10 mL vial was equipped with a stir bar. Compounds PLC-12.1 (30.0 mg, 0.051 mmol), PLC-12.2 (29.8 mg, 0.064 mmol), EDC·HCl (48.9 mg, 0.255 mmol), and DMAP·TsOH (30.6 mg, 0.102 mmol) were added to the vial, followed by anhydrous DCM (1.5 mL). The reaction mixture was heated to 40 °C overnight. After cooling to room temperature, the reaction mixture was loaded onto silica gel and purified by flash chromatography using DCM in EtOAc (0% → 5%) as the eluent to afford pure RL-naphthalimide-BODIPY PLC-12 as a dark green solid. The solid was further triturated with MeOH (10 mL) to afford RL-naphthalimide-BODIPY PLC-12 (31.0 mg, 61% yield). MS(APCI):C 59 H 38 Calculated for BClFN0S ([M+H] + )=1005 Actual value: 1005. 1 H NMR(400MHz, CDCl3) 8.81(m,2H), 8.68(d,J=8.0Hz,1H), 8.48(d,J=8.0Hz,1H), 8.26(m,2H), 7.56(d,J=8.0Hz,1H), 7.43(m,7H), 7.31(m,6H), 7.2 5(m,2H), 6.37(s,2H), 2.93(m,4H), 2.87(d,J=7.6Hz,2H), 2.69(m,6H), 2.24(s,6H), 2.19(ddd,J=7.6Hz,7.6Hz,7.6Hz,2H).

[0233] Synthesis of PLC-13: [ka]

[0234] General procedure for PLC-13: A 10 mL vial was equipped with a stir bar. Compounds PLC-13.1 (30.0 mg, 0.058 mmol), PLC-13.2 (33.8 mg, 0.073 mmol), EDC·HCl (55.6 mg, 0.290 mmol), and DMAP·TsOH (34.8 mg, 0.116 mmol) were added to the vial, followed by anhydrous DCM (1.5 mL). The reaction mixture was heated to 40 °C overnight. After cooling to room temperature, the reaction mixture was loaded onto silica gel and purified by flash chromatography using DCM in EtOAc (0% → 5%) as the eluent to afford pure RL-naphthalimide-BODIPY PLC-13 as a dark green solid. The solid was further triturated with MeOH (10 mL) to afford RL-naphthalimide-BODIPY PLC-13 (29.0 mg, 52% yield). MS(APCI):C 61 H 44 Calculated value for BF2N3O4S ([MH] - )=963 Actual value: 963. 1 H NMR(400MHz, CDCl3) 8.81(m,2H), 8.68(d,J=8.0Hz,1H), 8.48(d,J=8.0Hz,1H), 8.26(m,2H), 7.56(d,J=8.0Hz,1H), 7.43(m,9H), 7.2 9(m,6H), 7.24(m,2H), 2.88(m,6H), 2.72(t,J=7.2Hz,2H), 2.54(m,4H), 2.21(ddd,J=7.2Hz,7.2Hz,7.2Hz,2H).

[0235] Synthesis of PLC-14: [ka]

[0236] General procedure for PLC-14: A 10 mL vial was equipped with a stir bar. Compounds PLC-14.1 (30.0 mg, 0.055 mmol), PLC-14.2 (31.8 mg, 0.068 mmol), EDC·HCl (52.7 mg, 0.275 mmol), and DMAP·TsOH (33.0 mg, 0.110 mmol) were added to the vial, followed by anhydrous DCM (1.5 mL). The reaction mixture was heated to 40 °C overnight. After cooling to room temperature, the reaction mixture was loaded onto silica gel and purified by flash chromatography using DCM in EtOAc (0% → 5%) as the eluent to afford pure RL-naphthalimide-BODIPY PLC-14 as a dark green solid. The solid was further triturated with MeOH (10 mL) to afford RL-naphthalimide-BODIPY PLC-14 (44.0 mg, 80% yield). MS(APCI):C 61 H 44 Calculated value for BF2N3O6S ([MH] - )=995 Actual value: 995. 1 H NMR(400MHz, CDCl3) 8.81(m,2H), 8.68(d,J=8.0Hz,1H), 8.48(d,J=8.0Hz,1H), 8.26(m,2H), 7.56(d,J=8.0Hz,1H), 7.44(m,7H), 7.29(m,4H) , 7.23(m,2H), 6.46(s,2H), 6.42(s,2H), 3.73(s,6H), 2.89(m,6H), 2.68(m,6H), 2.21(ddd,J=7.6Hz,7.6Hz,7.6Hz,2H).

[0237] Synthesis of PLC-15: [ka]

[0238] General procedure for PLC-15: A 10 mL vial was equipped with a stir bar. Compounds PLC-15.1 (22.0 mg, 0.037 mmol), PLC-15.2 (20.7 mg, 0.046 mmol), EDC·HCl (35.5 mg, 0.185 mmol), and DMAP·TsOH (22.2 mg, 0.074 mmol) were added to the vial, followed by anhydrous DCM (1.5 mL) and THF (1.5 mL). The reaction mixture was heated to 60 °C overnight. After cooling to room temperature, the reaction mixture was loaded onto silica gel and purified by flash chromatography using DCM in EtOAc (0% → 5%) as the eluent to afford pure RL-naphthalimide-BODIPY PLC-15 as a dark green solid. The solid was further triturated with MeOH (10 ml) to give RL-naphthalimide-BODIPY PLC-15 (6.0 mg, 16% yield). MS (APCI): C 67 H 52 Calculated value for BF2N3O5 ([MH] - )=1027 Actual value: 1027. 1 H NMR(400MHz, CDCl3) 8.68(d,J=8.0Hz,1H), 8.64(d,J=8.0Hz,1H), 8.30(m,2H), 8.11(dd,J=8.0Hz,J=1.6Hz,1H), 7.99(d,J=8.0Hz,1H), 7.56(td,J=8.0Hz,J=1.6Hz, 1H), 7.41(m,10H), 7.31(m,3H), 7.00(s,2H), 6.19(s,2H), 2.89(t,J=7. 6Hz,2H), 2.71(t,J=7.6Hz,2H), 2.51(s,6H), 2.21(m,2H), 1.98(m,16H).

[0239] Synthesis of PLC-16: [ka]

[0240] General procedure for PLC-16.3: A 100 mL two-neck round-bottom flask was equipped with an air condenser and a stir bar. Compounds 1,4,5,6-tetrahydrobenzo[6,7]cyclohepta[1,2-b]pyrrole PLC-16.1 (542.0 mg, 2.96 mmol) and 4-hydroxy-2,6-difluorobenzaldehyde PLC-16.2 (222.6 mg, 1.4 mmol) were added to the flask, followed by anhydrous dichloromethane (20 mL). The reaction mixture was sparged with Ar for 30 minutes, and then p-TsOH·HO (17.0 mg, 0.14 mmol) was added. The reaction solution was stirred at room temperature for 2 hours. After complete consumption of the aldehyde starting material, DDQ (381.4 mg, 1.68 mmol) was added. The reaction was held at room temperature for 1 hour. EtN (1.2 mL, 8.40 mmol) was then added and the reaction was kept at room temperature for 30 minutes, followed by the addition of BF·OEt (2.1 mL, 12.6 mmol). The reaction mixture was kept at room temperature for an additional hour. The reaction mixture was loaded onto silica gel and purified by flash chromatography using DCM in hexanes (0% → 80% → 90%) as the eluent to give pure BODIPY PLC-16.3 as a blue-gold solid (279.0 mg, 36% yield). MS (APCI): C 33 H 25 Calculated value for BF4N2O ([MH] - )=552 Actual value: 552.

[0241] General procedure for PLC-16: A 10 mL vial was equipped with a stir bar. Compounds PLC-16.3 (30.0 mg, 0.054 mmol), PLC-16.4 (30.5 mg, 0.068 mmol), EDC·HCl (51.8 mg, 0.270 mmol), and DMAP·TsOH (32.4 mg, 0.108 mmol) were added to the vial, followed by anhydrous DCM (1.5 mL). The reaction mixture was heated to 40 °C overnight. After cooling to room temperature, the reaction mixture was loaded onto silica gel and purified by flash chromatography using DCM in EtOAc (0% → 5%) as the eluent to afford pure RL-naphthalimide-BODIPY PLC-16 as a green-purple solid. The solid was further triturated with MeOH (10 mL) to afford RL-naphthalimide-BODIPY PLC-16 (25.0 mg, 47% yield). MS(APCI):C 61 H 42 Calculated value for BF4N3O5 ([MH] - )=983 Actual value: 983. 1 H NMR(400MHz,CDCl2CDCl2) 8.65(d,J=8.0Hz,1H), 8.61(d,J=8.0Hz,1H), 8.13(dd,J=8.0Hz,J=1.6Hz,1H), 8.02(m,3H), 7.60(td,J=8.0Hz,J=1.6Hz,1H), 7.39(m,1 3H), 7.04(m,2H), 6.63(s,2H), 2.91(t,J=7.2Hz,2H), 2.77(t,J=7.2Hz,2H), 2.64(m,4H), 2.70(dd,J=6.8Hz,J=6.8Hz,6H), 2.20(m,9H).

[0242] Synthesis of PLC-17: [ka]

[0243] General procedure for PLC-17.3: A 100 mL two-neck round-bottom flask was equipped with an air condenser and a stir bar. Compounds 4,5-dihydro-1H-benzo[g]indole PLC-17.1 (507.7 mg, 3.0 mmol) and 4-hydroxy-2,6-difluorobenzaldehyde PLC-17.2 (225.9 mg, 1.43 mmol) were added to the flask, followed by anhydrous dichloromethane (20 mL). The reaction mixture was sparged with Ar for 30 minutes, and then p-TsOH·HO (17.4 mg, 0.143 mmol) was added. The reaction solution was stirred at room temperature for 2 hours. After complete consumption of the aldehyde starting material, DDQ (392.4 mg, 1.74 mmol) was added. The reaction was held at room temperature for 1 hour. EtN (1.2 mL, 8.64 mmol) was then added and the reaction was kept at room temperature for 30 minutes, followed by the addition of BF·OEt (1.6 mL, 12.96 mmol) at room temperature. The reaction mixture was kept at room temperature for an additional hour. The reaction mixture was loaded onto silica gel and purified by flash chromatography using DCM in hexanes (0% → 80% → 90%) as the eluent to give pure BODIPY PLC-17.3 as a golden brown solid (211.0 mg, 28% yield). MS (APCI): C 31 H 21 Calculated value for BF4N2O ([MH] - )=524 Actual value: 524. 1 H NMR (400MHz, CDCl3) 8.80(d,J=8.0Hz,2H), 7.44(m,2H), 7.32(m,2H), 7.23(m,2H), 6.57(m,2H), 6.49(s,2H), 2.92(m,4H), 2.69(m,4H).

[0244] General procedure for PLC-17: A 10 mL vial was equipped with a stir bar. Compounds PLC-17.3 (30.0 mg, 0.057 mmol), PLC-17.4 (32.1 mg, 0.072 mmol), EDC·HCl (54.6 mg, 0.285 mmol), and DMAP·TsOH (34.2 mg, 0.114 mmol) were added to the vial, followed by anhydrous DCM (1.5 mL). The reaction mixture was heated to 40 °C overnight. After cooling to room temperature, the reaction mixture was loaded onto silica gel and purified by flash chromatography using DCM in EtOAc (0% → 5%) as the eluent to afford pure RL-naphthalimide-BODIPY PLC-17 as a dark green solid. The solid was further triturated with MeOH (10 mL) to afford RL-naphthalimide-BODIPY PLC-17 (38.0 mg, 70% yield). MS(APCI):C 59 H 38 Calculated value for BF4N3O5 ([MH] - )=955 Actual value: 955. 1 H NMR(400MHz, CDCl3) 8.80(m,2H), 8.68(d,J=8.0Hz,1H), 8.64(d,J=8.0Hz,1H), 8.11(dd,J=8.0Hz,J=1.6Hz,1H), 7.99(d,J=8.0Hz,1H), 7.56(td,J=8.0 Hz,J=1.6Hz,1H), 7.38(m,12H), 7.24(m,1H), 6.94(m,2H), 6.50(s,2H), 2.90(m,6H), 2.70(dd,J=6.8Hz,J=6.8Hz,6H), 2.19(m,2H).

[0245] Synthesis of PLC-18: [ka]

[0246] General procedure for PLC-18: A 10 mL vial was equipped with a stir bar. Compounds PLC-18.1 (30.0 mg, 0.054 mmol), PLC-18.2 (31.6 mg, 0.068 mmol), EDC·HCl (51.8 mg, 0.270 mmol), and DMAP·TsOH (32.4 mg, 0.108 mmol) were added to the vial, followed by anhydrous DCM (1.5 mL). The reaction mixture was heated to 40 °C overnight. After cooling to room temperature, the reaction mixture was loaded onto silica gel and purified by flash chromatography using DCM in EtOAc (0% → 5%) as the eluent to afford pure RL-naphthalimide-BODIPY PLC-18 as a dark purple solid. The solid was further triturated with MeOH (10 mL) to afford RL-naphthalimide-BODIPY PLC-18 (43.0 mg, 78% yield). MS(APCI):C 63 H 48 Calculated value for BF2N3O6S ([MH] - )=1023 Actual value: 1023. 1 H NMR (400 MHz, CDCl3) 8.68(d,J=8.0Hz,1H), 8.47(d,J=8.0Hz,1H), 8.26(m,2H), 8.11(m,2H), 7.56(d,J=8.0Hz,1H), 7.44(m,5H), 7.31(m,6H), 7.21(m,2H), 6.50(s,2H) ), 6.49(s,2H), 3.77(s,6H), 2.89(t,J=7.2Hz,2H), 2.71(t,J=7.2Hz,2H), 2.62(m,4H), 2.28(m,6H), 2.02(ddd,J=7.2Hz,J=7.2Hz,J=7.2Hz,4H).

[0247] Synthesis of PLC-19: [ka]

[0248] General procedure for PLC-19: A 10 mL vial was equipped with a stir bar. Compounds PLC-19.1 (30.0 mg, 0.057 mmol), PLC-19.2 (33.3 mg, 0.072 mmol), EDC·HCl (54.6 mg, 0.285 mmol), and DMAP·TsOH (34.2 mg, 0.114 mmol) were added to the vial, followed by anhydrous DCM (1.5 mL). The reaction mixture was heated to 40 °C overnight. After cooling to room temperature, the reaction mixture was loaded onto silica gel and purified by flash chromatography using DCM in EtOAc (0% → 5%) as the eluent to afford pure RL-naphthalimide-BODIPY PLC-19 as a dark blue-green solid. The solid was further triturated with MeOH (10 mL) to afford RL-naphthalimide-BODIPY PLC-19 (43.0 mg, 78% yield). MS(APCI):C 59 H 38 Calculated value for BF4N3O4S ([MH] - )=971 Actual value: 971. 1 H NMR(400MHz, CDCl3) 8.80(m,2H), 8.67(d,J=8.0Hz,1H), 8.47(d,J=8.0Hz,1H), 8.25(m,2H), 7.56(d,J=8.0Hz,1H), 7.44(m,7H), 7.31(m ,5H), 7.24(m,1H), 6.94(m,2H), 6.50(s,2H), 2.91(m,6H), 2.70(m,6H), 2.20(ddd,J=7.6Hz,J=7.6Hz,J=7.6Hz,4H).

[0249] Synthesis of PLC-20: [ka]

[0250] General procedure for PLC-20: A 10 mL vial was equipped with a stir bar. Compounds PLC-20.1 (30.0 mg, 0.054 mmol), PLC-20.2 (31.6 mg, 0.068 mmol), EDC·HCl (51.8 mg, 0.270 mmol), and DMAP·TsOH (32.4 mg, 0.108 mmol) were added to the vial, followed by anhydrous DCM (1.5 mL). The reaction mixture was heated to 40 °C overnight. After cooling to room temperature, the reaction mixture was loaded onto silica gel and purified by flash chromatography using DCM in EtOAc (0% → 5%) as the eluent to afford pure RL-naphthalimide-BODIPY PLC-20 as a dark blue-green solid. The solid was further triturated with MeOH (10 mL) to afford RL-naphthalimide-BODIPY PLC-20 (30.0 mg, 56% yield). MS(APCI):C 61 H 42 Calculated value for BF4N3O4S ([MH] - )=999 Actual value: 999. 1 H NMR(400MHz,CDCl2CDCl2) 8.65(d,J=8.0Hz,1H), 8.44(d,J=8.0Hz,1H), 8.28(m,2H), 8.03(m,2H), 7.61(d,J=8.0Hz,1H), 7.47(m,5H), 7.33(m, 8H), 7.04(m,2H), 6.63(s,2H), 2.91(t,J=7.2Hz,2H), 2.76(t,J=7.2Hz,2H), 2.64(m,4H), 2.35(bs,3H), 2.13(m,6H).

[0251] Synthesis of PLC-21: [ka]

[0252] General procedure for PLC-21: A 10 mL vial was equipped with a stir bar. Compounds PLC-21.1 (30.0 mg, 0.055 mmol), PLC-21.2 (31.0 mg, 0.069 mmol), EDC·HCl (52.7 mg, 0.275 mmol), and DMAP·TsOH (33.0 mg, 0.110 mmol) were added to the vial, followed by anhydrous DCM (1.5 mL). The reaction mixture was heated to 40 °C overnight. After cooling to room temperature, the reaction mixture was loaded onto silica gel and purified by flash chromatography using DCM in EtOAc (0% → 5%) as the eluent to afford pure RL-naphthalimide-BODIPY PLC-21 as a dark blue-green solid. The solid was further triturated with MeOH (10 mL) to afford RL-naphthalimide-BODIPY PLC-21 (39.0 mg, 72% yield). MS(APCI):C 63 H 48 Calculated value for BF2N3O5 ([MH] - )=975 Actual value: 975.1H NMR(400MHz,CDCl2CDCl2) 8.76(m,2H), 8.66(d,J=8.0Hz,1H), 8.61(d,J=8.0Hz,1H), 8.13(dd,J=8.0Hz,J=1.6Hz,1H), 8.02(d,J=8.0Hz,1H), 7.60(td,J=8.0H) z,J=1.6Hz,1H), 7.38(m,13H), 7.01(s,2H), 2.91(m,6H), 2.72(t,J=7.2Hz,2H), 2.57(m,4H), 2.25(s,6H), 2.23(m,2H), 1.42(s,6H).

[0253] Synthesis of PLC-22: [ka]

[0254] General procedure for PLC-22: A 10 mL vial was equipped with a stir bar. Compounds PLC-22.1 (30.0 mg, 0.055 mmol), PLC-22.2 (29.0 mg, 0.069 mmol), EDC·HCl (52.7 mg, 0.275 mmol), and DMAP·TsOH (33.0 mg, 0.110 mmol) were added to the vial, followed by anhydrous DCM (1.5 mL). The reaction mixture was heated to 40 °C overnight. After cooling to room temperature, the reaction mixture was loaded onto silica gel and purified by flash chromatography using DCM in EtOAc (0% → 5%) as the eluent to afford pure RL-naphthalimide-BODIPY PLC-22 as a dark blue-green solid. The solid was further triturated with MeOH (10 mL) to afford RL-naphthalimide-BODIPY PLC-22 (33.0 mg, 63% yield). MS(APCI):C 61 H 44 Calculated value for BF2N3O5 ([MH] - )=947 Actual value: 947. 1 H NMR(400MHz,CDCl2CDCl2) 8.67(d,J=8.0Hz,1H), 8.62(d,J=8.0Hz,1H), 8.14(dd,J=8.0Hz,J=1.6Hz,1H), 8.05(m,2H), 8.02(d,J=8.0Hz,1H), 7.66(m,2H) , 7.60(td,J=8.0Hz,J=1.6Hz,1H), 7.37(m,11H), 7.01(s,2H), 6.46(s,2H), 4.04(s,2H), 2.63(m,4H), 2.30(m,9H), 2.04(m,4H).

[0255] Synthesis of PLC-23: [ka]

[0256] General procedure for PLC-23: A 10 mL vial was equipped with a stir bar. Compounds PLC-23.1 (30.0 mg, 0.051 mmol), PLC-23.2 (27.0 mg, 0.064 mmol), EDC·HCl (48.9 mg, 0.255 mmol), and DMAP·TsOH (30.6 mg, 0.102 mmol) were added to the vial, followed by anhydrous DCM (1.5 mL). The reaction mixture was heated to 40 °C overnight. After cooling to room temperature, the reaction mixture was loaded onto silica gel and purified by flash chromatography using DCM in EtOAc (0% → 5%) as the eluent to afford pure RL-naphthalimide-BODIPY PLC-23 as a dark blue-green solid. The solid was further triturated with MeOH (10 mL) to afford RL-naphthalimide-BODIPY PLC-23 (17.0 mg, 34% yield). MS(APCI):C 59 H 38 Calculated value for BCl2F2N3O5 ([MH] - )=988 Actual value: 988. 1 H NMR(400MHz,CDCl2CDCl2) 8.67(d,J=8.0Hz,1H), 8.62(d,J=8.0Hz,1H), 8.14(dd,J=8.0Hz,J=1.6Hz,1H), 8.05(m,2H), 8.03(d,J=8.0Hz,1H), 7.65(m,2H), 7.60(td,J=8.0Hz,J=1.6Hz,1H), 7.43(s,2H), 7.38(m,11H), 6.48(s,2H), 4.06(s,2H), 2.64(m,4H), 2.33(bs,3H), 2.05(m,4H).

[0257] Synthesis of PLC-24: [ka]

[0258] General procedure for PLC-24: A mixture of compound PLC-24.1 (16 mg, 0.027 mmol), compound PLC-24.2 (19 mg, 0.04 mmol), EDC·HCl (52 mg, 0.27 mmol), and DMAP / p-TsOH (8 mg, 0.027 mmol) in DCM (5 mL) was stirred overnight at room temperature. The resulting mixture was then loaded onto silica gel and purified by flash chromatography using an eluent of hexane / DCM (50% → 100% DCM) followed by DCM / ethyl acetate (0% → 5% ethyl acetate). The main red fraction was collected and concentrated under reduced pressure. The resulting solid was triturated with methanol, filtered, and air-dried to give a dark red solid (18 mg, 64.6% yield). LCMS (APCI-): C 61 H 42 Calculated for BCl2F2N3O4S (M-) = 1031.23; Found: 1031. 1 H NMR(400MHz,d2-TCE) δ 8.56(d,J=8.2Hz,1H), 8.35(d,J=8.0Hz,1H), 8.19(dd,J=8.8,4.5Hz,2H), 7.97(s, 2H), 7.51(d,J=8.0Hz,1H), 7.38(dt,J=7.3,2.4Hz,5H), 7.29(d,J=9.3Hz,6H), 7.2 4~7.15(m,4H), 6.40(s,2H), 2.82(t,J=7.5Hz,2H), 2.67(t,J=7.4Hz,2H), 2.54(d, J=6.8Hz,4H), 2.24(s,4H), 2.11(td,J=13.4,11.8,5.9Hz,2H), 2.04~1.89(m,4H).

[0259] Synthesis of PLC-25: [ka]

[0260] General procedure for PLC-25: A mixture of compound PLC-2.1 (20 mg, 0.034 mmol), compound Ex-5 (27 mg, 0.051 mmol), EDC·HCl (60 mg, 0.31 mmol), and DMAP / p-TsOH (8.8 mg, 0.03 mmol) in DCM (4 mL) was stirred overnight at room temperature. The resulting mixture was then loaded onto silica gel and purified by flash chromatography using an eluent of DCM / ethyl acetate (0% → 10% ethyl acetate). The main red fraction was collected and concentrated under reduced pressure to 0.5 mL, followed by the addition of 10 mL of methanol. The resulting precipitate was filtered and dried in air to give a dark red solid (23 mg, 62% yield). LCMS (APCI-): C 69 H 44 Calculated for BCl2F8N3O5 (M-) = 1227.26; Found: 1227. 1 H NMR(400MHz,d2-TCE) δ 8.58(dd,J=19.5,8.1Hz,2H), 8.18(d,J=2.2Hz,1H), 8.06(d,J=8.1Hz,1H), 8.02(d,J=1.5Hz,2H),7. 97(t,J=4.6Hz,2H), 7.87(s,1H), 7.72(dd,J=8.6,2.1Hz,1H), 7.49(d,J=8.6Hz,1H), 7.39(d,J=8.2H z,2H), 7.34(d,J=8.3Hz,1H), 7.32~7.25(m,6H), 7.25~7.18(m,4H), 6.40(s,2H), 2.82(t,J=7.5Hz,2 H), 2.67(t,J=7.4Hz,2H), 2.61~2.50(m,4H), 2.24(s,4H), 2.13(q,J=7.4Hz,2H), 2.04~1.90(m,4H).

[0261] Synthesis of PLC-26: [ka]

[0262] Compound PLC-26.1 (6-(4-(tert-butyl)-2-nitrophenoxy)-1H,3H-benzo[de]isochromene-1,3-dione): A 1 L, two-neck, round-bottom flask was equipped with a stir bar and placed in an aluminum heat block. The flask was fitted with a finned condenser, a gas adapter, and a flow controller. The flask was flushed with argon. To the flask was added 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, 11.712 g), NaOH (20.0 mmol, 800 mg), copper powder (20.0 mmol, 1.271 g), and anhydrous NMP (150 mL). The flask was closed and stirred under argon. The heat block was set to 170°C and the reaction mixture was heated at this temperature overnight. LCMS indicated the reaction was complete. The reaction mixture was cooled to room temperature. To the flask was added 1N HCl (44 mL) and water (175 mL). After stirring for approximately 15 minutes, the resulting precipitate was filtered off and washed with water. The dried precipitate was dissolved in hot ethyl acetate and filtered hot to remove a small amount of insoluble material. The ethyl acetate was removed in vacuo. The resulting solid was triturated with hot methanol and then cooled to room temperature. The resulting precipitate was filtered off and washed with methanol. The solid was dried in a vacuum oven at 100°C. 8.18 g (52% yield) was obtained. MS (APCI): C 22 H 17 Calculated for NO (M+H) = 392; found: 392. 1H NMR (400 MHz, tetrachloroethane-d2) δ 8.82 (dd, J = 8.5, 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, 2.4 Hz, 1H), 7.34 (d, J = 8.6 Hz, 1H), 6.91 (d, J = 8.3 Hz, 1H), 1.43 (s, 9H).

[0263] Compound PLC-26.2 (6-(2-amino-4-(tert-butyl)phenoxy)-1H,3H-benzo[de]isochromene-1,3-dione): A 250 mL two-neck round-bottom flask was equipped with a stir bar, a finned condenser, a gas adapter, and a flow controller. The flask was placed in an aluminum heat block. The flask was flushed with argon. Compound PLC-26.1 (10.0 mmol, 3.914 g) and SnCl 2H O (40.0 mmol, 9.024 g) were added to the flask, followed by 2-methyl THF (70 mL) and concentrated hydrochloric acid (4.0 M) (100 mmol, 25 mL). The flask was closed and heated to 90 °C under argon for 30 minutes, at which point TLC indicated complete conversion to the product. The reaction mixture was cooled to room temperature, and then the pH was adjusted to pH 8 using 2 N NaOH. The resulting precipitate was filtered off. The solid was extracted with 2-methyl THF (8 x 100 mL). The layers were separated and the organic layer was dried over MgSO4, filtered and evaporated to dryness. The resulting solid was dried at 120°C. The product was obtained in quantitative yield. MS (APCI): C 22 H 19 Calculated for NO (M+H) = 362; found: 362. 1H NMR (400 MHz, tetrachloroethane-d2) 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 = 8.4 Hz, 1H), 7.89 (dd, J = 8.4, 7.3 Hz, 1H), 7.03 to 6.93 (m, 3H), 6.88 (dd, J = 8.4, 2.3 Hz, 1H), 1.35 (s, 9H).

[0264] Compound PLC-26.3 (9-(tert-butyl)-1H,3H-isochromeno[6,5,4-mna]xanthene-1,3-dione): A 40 mL vial was charged with NaNO (30.0 mmol, 2.070 g), water (10 mL), and a stir bar. The vial was placed in an ice-water bath and stirred to dissolve. A 100 mL round-bottom flask was charged with a stir bar and compound PLC-26.2 (4.00 mmol, 1.446 g), hydrochloric acid (37%) (20.0 mmol, 12.1 M, 1.65 mL), and glacial acetic acid (30 mL). The flask was lowered into an ice-water bath and stirred for approximately 1 minute, after which the addition of the sodium nitrite solution was begun in small increments over 3 minutes. The solution was stirred in the ice-water bath for 1 hour. A 1 L, two-neck round-bottom flask was clamped with its neck offset at an angle so that a dropping funnel inserted into the neck fell onto the top of a stirred vortex. A finned condenser was attached to the other neck. To this flask was added a large stir bar, CuSO4·5H2O (27.4 mmol, 6.842 g), and water (80 mL). Near the end of the 1-hour waiting period for the diazo salt, the copper(II) solution was placed in an aluminum heat block and the temperature was set to 130 °C. When the copper(II) solution reached 130 °C, the diazo solution was transferred to the dropping funnel. The reaction was stirred at maximum RPM, and the diazo solution was added dropwise over approximately 20 minutes. The resulting solution was stirred at 130 °C for 2 minutes, then removed from the heat block and stirred overnight at room temperature. The precipitate was filtered off and washed with water. The crude precipitate was dried, then dissolved and evaporated in vacuo onto silica gel. Purification was by column chromatography on silica gel (220 g, equilibrated with 50% hexane / DCM, elution 50% (2 CV) → 100% DCM (20 CV), isocratic DCM (15 CV) → 0% EtOAc / DCM (0 CV) → 1% EtOAc / DCM (10 CV)). Product tail. All fractions containing product were collected and evaporated to dryness in vacuo. 528 mg (38% yield) was obtained. MS (APCI): C 22 H 16Calculated for O4 (M+H) = 345; found: 345. 1H NMR (400 MHz, tetrachloroethane-d2) δ 8.61 (d, J = 7.9 Hz, 1H), 8.56 (d, J = 8.4 Hz, 1H), 8.05 (d, J = 2.2 Hz, 1H), 8.01 (d, J = 8.0 Hz, 1H), 7.66 (dd, J = 8.8, 2.2 Hz, 1H), 7.38 (d, J = 8.7 Hz, 1H), 7.34 (d, J = 8.4 Hz, 1H), 1.44 (s, 9H).

[0265] Compound PLC-26.4 (4-(4-(9-(tert-butyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)butanoic acid): A 100 mL two-neck round-bottom flask (RBF) was equipped with a stir bar, a finned condenser, a gas adapter, and a flow control valve. The flask was flushed with argon and charged with compound PLC-26.3 (1.525 mmol, 525 mg), 4-(4-aminophenyl)butanoic acid (3.05 mmol, 546 mg), and DMAP (0.1113 mmol, 14 mg). Anhydrous DMF (10 mL) was added to the flask. The flask was sealed and stirred under argon. A heat block was set to 175 °C and the reaction was heated and stirred for 6.5 h, then at room temperature overnight. Acetone (25 mL) and water (25 mL) were added to the reaction mixture. The precipitate was stirred for 5 minutes, then filtered off and washed with 1:1 water:acetone. The precipitate was dried at 120° C. under a stream of argon. 738 mg (96% yield) was obtained. MS (APCI): C 32 H 27 Calculated for NO5 (M+H) = 506; found: 506. 1H NMR (400 MHz, DMSO-d6) δ 12.12 (s, 1H), 8.48–8.29 (m, 3H), 8.23 ​​(d, J = 2.3 Hz, 1H), 7.68 (dd, J = 8.8, 2.3 Hz, 1H), 7.43–7.30 (m, 4H), 7.25 (d, J = 7.9 Hz, 2H), 2.75–2.64 (m, 2H), 2.30 (t, J = 7.4 Hz, 2H), 1.88 (p, J = 7.5 Hz, 2H), 1.41 (s, 9H).

[0266] Compound PLC-26 (3,5-dichloro-4-(19,19-difluoro-6,7,11,12,13,19-hexahydro-5H-18|4,19|4-benzo[3',4']cyclohepta[1',2':4,5]pyrrolo[1,2-c]benzo[3',4']cyclohepta[1',2':4,5]pyrrolo[2,1-f][1,3,2]diazaborin-9-yl)phenyl 4-(4-(9-(tert-butyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)butanoate): Place a stir bar, 3,5-dichloro-4-(19,19- Difluoro-6,7,11,12,13,19-hexahydro-5H-18|4,19|4-benzo[3',4']cyclohepta[1',2':4,5]pyrrolo[1,2-c]benzo[3',4']cyclohepta[1',2':4,5]pyrrolo[2,1-f][1,3,2]diazaborin-9-yl)phenol (0.050 mmol, 29.3 mg), compound PLC-26.4 (0.075 mmol, 37.9 mg), DMAP·pTsOH salt (0.100 mmol, 29.4 mg), and EDC·HCl (0.075 mmol, 14.4 mg) were added to the vial, which was then capped and stirred at room temperature for 4.5 h. The reaction mixture was diluted with hexane (to approximately 35 mL) and loaded onto a solid cartridge (approximately 20 g of SiO2). The reaction mixture was purified by column chromatography on silica gel (120 g, equilibrated with 100% toluene, eluting with 100% (5 CV) → 5% EtOAc / toluene (30 CV)). The product-containing fractions were evaporated to dryness and repurified by flash chromatography on silica gel (solid, 120 g column, equilibrated with 40% DCM / hexane, eluting with 40% (2 CV) → 100% DCM (10 CV) → isocratic DCM (until the compound was completely eluted)). The product-containing fractions were evaporated to dryness in vacuo. 19.8 mg (37% yield) was obtained. MS (APCI): C 65 H 50Calculated for BCl2F2N3O5 (M-) = 1071; found: 1071. 1H NMR (400 MHz, methylene chloride-d2) δ 8.65 (d, J = 7.9 Hz, 1H), 8.58 (d, J = 8.3 Hz, 1H), 8.12 (d, J = 2.3 Hz, 1H), 8.05 (d, J = 8.0 Hz, 1H), 8.00 (d, J = 6.8 Hz, 2H), 7.63 (dd, J = 8.7, 2.3 Hz, 1H), 7.47-7.43 (m, 2H), 7.40 (s, 2H), 7.63 (dd, J = 8.7, 2.3 Hz, 1H). 38~7.24(m,10H), 6.51(s,2H), 2.90(t,J=7.6Hz,2H), 2.75(t,J=7.4Hz,2H), 2.64(t,J=6 .8Hz,4H), 2.43~2.26(m,4H), 2.21(p,J=7.5Hz,2H), 2.05(p,J=7.0Hz,4H), 1.44(s,9H).

[0267] Synthesis of PLC-27: [ka]

[0268] Compound PLC-27.2 (2-(4-(9-(tert-butyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid): Compound PLC-27.2 was synthesized in a manner similar to compound PLC-26.4 from compound PLC-27.1 (1.191 mmol, 410 mg), 2-(4-aminophenyl)acetic acid (2.98 mmol, 450 mg), and DMAP (0.0869 mmol, 11 mg). The product was obtained in quantitative yield. MS (APCI): C 30 H 23 Calculated for NO5 (M+H) = 478; found: 478. 1H NMR (400 MHz, DMSO-d6) δ 8.48 (d, J = 7.9 Hz, 1H), 8.44 (d, J = 8.3 Hz, 1H), 8.38 (d, J = 8.1 Hz, 1H), 8.27 (d, J = 2.4 Hz, 1H), 7.69 (dd, J = 8.8, 2.3 Hz, 1H), 7.45-7.38 (m, 4H), 7.31-7.27 (m, 2H), 3.68 (s, 2H), 1.41 (s, 9H).

[0269] Compound PLC-27 (3,5-dichloro-4-(19,19-difluoro-6,7,11,12,13,19-hexahydro-5H-18|4,19|4-benzo[3',4']cyclohepta[1',2':4,5]pyrrolo[1,2-c]benzo[3',4']cyclohepta[1',2':4,5]pyrrolo[2,1-f][1,3,2]diazaborin-9-yl)phenyl 2-(4-(9-(tert-butyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate: Compound PLC-27 was prepared by the reaction of 3,5-dichloro-4-(19,19-difluoro-6,7,11,12,13,19-hexahydro-5H-1814,1914-benzo[3',4'])cyclohepta[1',2':4,5]pyrrolo[1,2-c]benzo This reaction mixture was synthesized from [3',4']cyclohepta[1',2':4,5]pyrrolo[2,1-f][1,3,2]diazaborin-9-yl)phenol (0.100 mmol, 58.6 mg), PLC-27.2 (0.150 mmol, 71.6 mg), DMAP / pTsOH salt (0.200 mmol, 58.8 mg), and EDC / HCl (0.150 mmol, 28.8 mg), followed by anhydrous DCM (10 mL). The vial was capped and stirred overnight at room temperature. The next morning, additional EDC·HCl (0.200 mmol, 38.8 mg) was added and stirred at room temperature for 90 minutes. Additional EDC·HCl (0.200 mmol, 38.3 mg) was added and the mixture was stirred at room temperature for 2 hours. Compound PLC-27.2 (0.075 mmol, 35.8 mg) was added and stirring was continued at room temperature for 2 hours. The crude reaction mixture was purified by flash chromatography on silica gel (solid, 120 g column, equilibrated with 40% DCM / hexane, eluting with 40% (2 CV) → 100% DCM (10 CV) → isocratic DCM (until the compound was completely eluted)). The product-containing fractions were evaporated to dryness in vacuo. 11.0 mg (11% yield) was obtained. MS (APCI): C 63 H 46Calculated for BCl2F2N3O5 (M-) = 1043; Found: 1043. 1H NMR (400 MHz, methylene chloride-d2) δ 8.67(d,J=7.9Hz,1H), 8.60(d,J=8.4Hz,1H), 8.13(d,J=2.3Hz,1H), 8.07(d,J=8.0Hz,1H), 8.00(d,J=6.9Hz,2H), 7.64(dd,J=8.8,2.3Hz,1H),7. 62~7.58(m,2H), 7.44(s,2H), 7.40~7.27(m,10H), 6.51(s,2H), 4.07(s, 2H), 2.70~2.58(m,4H), 2.33(s,4H), 2.05(p,J=7.1Hz,4H), 1.44(s,9H).

[0270] Synthesis of compound PLC-28 [ka]

[0271] Compound PLC-28.2 2-(4-(9-Bromo-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid: A mixture of PLC-28.1 (400.0 mg, 1.1 mmol), 4-aminophenylacetic acid (329.4 mg, 2.2 mmol), and DMAP (9.3 mg, 0.080 mmol) in DMF (8 mL) was degassed at room temperature. The mixture was then heated to 165° C. and held at this temperature for 3 hours. TLC and LCMS showed approximately 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 held at 0° C. for 2 hours and then continued stirring 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 give pure compound PLC-28.2 as a tan solid (395.0 mg, 73% yield). MS (APCI): C 26 H 14 Calculated for BrNO5 ([M+H] +)=500 Actual value: 500.1H NMR(400MHz,CDCl2CDCl2) δ 8.65(d,J=8.0Hz,1H), 8.62(d,J=8.0Hz,1H), 8.21(dd,J=6.4Hz,2.4Hz,1H), 7.99(bs,1H), 7.95(t,J=7.6Hz ,1H), 7.67(dd,J=8.4Hz,2.4Hz,1H), 7.53(d,J=8.0Hz,2H), 7.37(d,J=8.4Hz,1H), 7.32(m,3H), 2.94(s,2H).

[0272] Compound PLC-28.3—2-(4-(9-(4-isopropylphenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid: A mixture of PLC-28.2 (175.0 mg, 0.35 mmol), 4-isopropylphenylboronic acid (114.8 mg, 0.70 mmol), Pd(dppf)Cl (18.0 mg, 0.025 mmol), and KCO (130.4 mg, 0.95 mmol) in THF-DMF-HO (10 mL / 2 mL / 1 mL) was degassed at room temperature. The mixture was then heated to 80° C. and maintained at this temperature overnight. TLC and LCMS indicated completion of the reaction. The mixture was cooled to room temperature. 0.1 N HCl (75 mL) and EtOAc (75 mL) were then added. After separation in a separatory funnel, the aqueous solution was saturated with NaCl and then further extracted with THF (75 mL x 3). The combined organic phases were dried over anhydrous NaSO, then filtered, concentrated on a rotary evaporator, and purified by silica gel flash chromatography using 0% to 40% EtOAc in DCM with 0.1% TFA as eluent to give PLC-28.3 (70.0 mg, 37% yield) as a yellow solid. MS (APCI): C 35 H 25 Calculated value for NO5 ([MH] - )=539;Actual value: 539. 1H NMR(400MHz,CDCl2CDCl2) δ 8.66(d,J=7.6Hz,1H), 8.61(d,J=8.4Hz,1H), 8.26(s,1H), 8.06(d,J=8.0Hz,1H), 7.79(dd,J=8. 4Hz,2.0Hz,1H), 7.45(m,11H), 3.81(s,2H), 3.01(quintet,J=7.2Hz,1H), 1.33(d,J=7.2Hz,6H).

[0273] Synthesis of Compound PLC-28: A 25 mL vial was equipped with a stir bar. Compounds PLC-28.4 (44.0 mg, 0.075 mmol), PLC-28.3 (81.0 mg, 0.15 mmol), EDC·HCl (71.9 mg, 0.38 mmol), and DMAP·TsOH (45.0 mg, 0.15 mmol) were added to the vial, followed by anhydrous DCM (4.4 mL). The reaction mixture was heated to 40 °C overnight. After cooling to room temperature, the reaction mixture was loaded onto silica gel and purified by flash chromatography using DCM in EtOAc (0% to 4%) as the eluent to afford pure RL-naphthalimide-BODIPY PLC-28 as a dark blue solid. The solid was further triturated with MeOH (15 mL) to afford RL-naphthalimide-BODIPY PLC-28 (46.0 mg, 55% yield). MS (APCI): C 68 H 48 Calculated value for BCl2F2N3O5 ([MH] - )=1106 Actual value: 1106. 1 H NMR(400MHz,CDCl2CDCl2) 8.67(d,J=8.0Hz,1H), 8.63(d,J=8.0Hz,1H), 8.29(d,J=2.4Hz,1H), 8.11(d,J= 8.0Hz,1H), 8.05(m,2H), 7.81(dd,J=8.0Hz,J=2.4Hz,1H), 7.65(m,4H), 7.51(d, J=8.0Hz,1H), 7.39(m,11H), 7.30(m,2H), 6.49(s,2H), 4.07(s,2H), 3.01(pente t,J=6.8Hz,1H), 2.64(m,4H), 2.33(bs,3H), 2.06(m,4H), 1.33(d,J=6.8Hz,6H).

[0274] Synthesis of compound PLC-29 [ka]

[0275] Compound 29. 1-2-(4-(1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid: A 100 mL vial was equipped with a stir bar. To the vial was added compound PLC-28.2 (400.0 mg, 0.80 mmol), 4-(trifluoromethyl)phenylboronic acid (262.2 mg, 1.6 mmol), Pd(dppf)Cl (41.0 mg, 0.056 mmol), and KCO (298.0 mg, 2.2 mmol) in THF / DMF / HO (22 mL / 4.4 mL / 2.2 mL) and degassed at room temperature. The reaction mixture was heated to 80 °C and maintained at this temperature overnight. The reaction was monitored using TLC. Upon completion, the reaction was worked up by adding 0.1N HCl (150 ml) and EtOAc (150 ml). The aqueous phase was further extracted with THF (150 ml x 3). The combined organic phases were dried over anhydrous NaSO, concentrated on a rotary evaporator, and purified by flash chromatography using DCM in EtOAc (0% to 40%, containing 0.1% TFA) as the eluent to afford the pure RL-naphthalimide derivative PLC-29.1 as a yellow / tan solid (363.0 mg, 80% yield). MS (APCI): C 33 H 18 Calculated value for F3NO5 ([M+H] + )=566 Actual value: 566. 1H NMR(400MHz,DMSO-d6) 8.76(m,1H), 8.56(m,2H), 8.52(dd,J=8.0Hz,J=3.2Hz,1H), 8.15(m,2H), 8.06(m,1H), 7.94(d,J=8.0Hz,2H ), 7.66(dd,J=8.0Hz,J=4.0Hz,1H), 7.53(m,1H), 7.45(d,J=8.0Hz,2H), 7.33(d,J=8.0Hz,2H), 3.72(s,2H).

[0276] Compound PLC-29: A 25 mL vial was equipped with a stir bar. Compound PLC-28.4 (40.0 mg, 0.068 mmol), PLC-29.1 (77.5 mg, 0.137 mmol), EDC·HCl (65.2 mg, 0.340 mmol), and DMAP·TsOH (41.1 mg, 0.137 mmol) were added to the vial, followed by anhydrous DCM (4 mL). The reaction mixture was heated to 40 °C overnight. After the reaction cooled to room temperature, the reaction mixture was loaded onto silica gel and purified by flash chromatography using DCM in EtOAc (0% to 4%) as the eluent to afford pure RL-naphthalimide-BODIPY PLC-29 as a dark blue solid. The solid was further triturated with MeOH (15 mL) to afford RL-naphthalimide-BODIPY PLC-29 (46.0 mg, 60% yield). MS (APCI): C 66 H 41 Calculated value for BCl2F5N3O5 ([MH] - )=1132 Actual value: 1132. 1 H NMR(400MHz,CDCl2CDCl2) 8.69(d,J=8.0Hz,1H), 8.65(d,J=8.0Hz,1H), 8.30(d,J=2.0Hz,1H), 8.11(d,J=8.0Hz,1H), 8.06(m,2H), 7.82(m,5H), 7.65( m,2H), 7.55(d,J=8.0Hz,1H), 7.39(m,9H), 7.30(m,2H), 6.48(s,2H), 4.07(s,2H), 2.63(m,4H), 2.33(bs,3H), 2.06(m,4H).

[0277] Synthesis of compound PLC-30 [ka]

[0278] Compound PLC-30.1—2-(4-(9-(3,5-bis(trifluoromethyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid: A 100 mL vial was equipped with a stir bar. To the vial was added compound PLC-28.2 (400.0 mg, 0.80 mmol), 3,5-bis(trifluoromethyl)phenylboronic acid (262.2 mg, 1.6 mmol), Pd(dppf)Cl (41.0 mg, 0.056 mmol), and KCO (412.6 mg, 2.2 mmol) in THF / DMF / HO (22 mL / 4.4 mL / 2.2 mL) and degassed at room temperature. The reaction mixture was heated to 80° C. and maintained at this temperature overnight. The reaction was monitored using TLC. Upon completion, the reaction was worked up by adding 0.1N HCl (150 ml) and EtOAc (150 ml). The aqueous phase was further extracted with THF (150 ml x 3). The combined organic phases were dried over anhydrous NaSO, concentrated on a rotary evaporator, and purified by flash chromatography using DCM in EtOAc (0% to 40%, containing 0.1% TFA) as the eluent to afford the pure RL-naphthalimide derivative PLC-30.1 as a yellow / tan solid (311.0 mg, 61% yield). MS (APCI): C 34 H 17 Calculated value for F6NO5 ([M+H] + )=634;Actual value: 634. 1 H 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).

[0279] Compound PLC-30: A 25 mL vial was equipped with a stir bar. Compound PLC-28.4 (40.0 mg, 0.068 mmol), PLC-30.1 (86.8 mg, 0.137 mmol), EDC·HCl (65.2 mg, 0.340 mmol), and DMAP·TsOH (41.1 mg, 0.137 mmol) were added to the vial, followed by anhydrous DCM (4 mL). The reaction mixture was heated to 40 °C overnight. After the reaction cooled to room temperature, the reaction mixture was loaded onto silica gel and purified by flash chromatography using DCM in EtOAc (0% to 4%) as the eluent to afford pure RL-naphthalimide-BODIPY PLC-30 as a dark blue solid. The solid was further triturated with MeOH (15 mL) to afford RL-naphthalimide-BODIPY PLC-30 (76.0 mg, 93% yield). MS (APCI): C 67 H 40 Calculated value for BCl2F8N3O5 ([MH] - )=1200 Actual value: 1200. 1 H NMR(400MHz,CDCl2CDCl2) 8.70(d,J=8.0Hz,1H), 8.66(d,J=8.0Hz,1H), 8.28(d,J=2.0Hz,1H), 8.15(d,J=8.0Hz,1H), 8.06(m,4H), 7.96(m,1H), 7.82(dd,J=8.0Hz,J=2 .0Hz,1H), 7.65(m,2H), 7.58(d,J=8.0Hz,1H), 7.39(m,9H), 7.30(m,2H), 6.48(s,2H), 4.07(s,2H), 2.63(m,4H), 2.33(bs,3H), 2.05(m,4H).

[0280] Synthesis of compound PLC-31 [ka]

[0281] Compound PLC-31.1-2-(4-(9-(4-(tert-butyl)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid: A mixture of PLC-28.2 (175.0 mg, 0.35 mmol), 4-tert-butylphenylboronic acid (124.6 mg, 0.70 mmol), Pd(dppf)Cl (18.0 mg, 0.025 mmol), and KCO (130.4 mg, 0.95 mmol) in THF-DMF-HO (10 mL / 2 mL / 1 mL) was degassed at room temperature. The mixture was then heated to 80 °C and maintained at this temperature overnight. TLC and LCMS indicated the reaction was complete. The mixture was cooled to room temperature. Then, 0.1N HCl (75 mL) and EtOAc (75 mL) were added. After separation in a separatory funnel, the aqueous solution was saturated with NaCl and then further extracted with THF (75 mL x 3). The combined organic phase was dried over anhydrous NaSO, which was then filtered, concentrated on a rotary evaporator, and purified by silica gel flash chromatography using 0% to 40% EtOAc in DCM with 0.1% TFA as the eluent to give PLC-31.1 as a yellow solid (76.0 mg, 39% yield). MS (APCI): C 36 H 27 Calculated value for NO5 ([MH] - )=553 Actual value: 553. 1 H NMR(400MHz,CDCl2CDCl2) δ 8.69(d,J=8.0Hz,1H), 8.64(d,J=8.4Hz,1H), 8.24(d,J=8.4Hz,1H), 8.03(d,J=8.0Hz,1 H), 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).

[0282] Compound PLC-31: A 25 mL vial was equipped with a stir bar. Compound PLC-28.4 (40.0 mg, 0.068 mmol), PLC-31.1 (75.8 mg, 0.137 mmol), EDC·HCl (65.2 mg, 0.340 mmol), and DMAP·TsOH (41.1 mg, 0.137 mmol) were added to the vial, followed by anhydrous DCM (4 mL). The reaction mixture was heated to 40 °C overnight. After the reaction cooled to room temperature, the reaction mixture was loaded onto silica gel and purified by flash chromatography using DCM in EtOAc (0% to 4%) as the eluent to afford pure RL-naphthalimide-BODIPY PLC-31 as a dark blue solid. The solid was further triturated with MeOH (15 mL) to afford RL-naphthalimide-BODIPY PLC-31 (40.0 mg, 52% yield). MS (APCI): C 69 H 50 Calculated value for BCl2F2N3O5 ([MH] - )=1120 Actual value: 1120. 1 H NMR(400MHz,CDCl2CDCl2)8.69(d,J=8.0Hz,1H), 8.63(d,J=8.0Hz,1H), 8.30(d,J=2.0Hz,1H), 8.11(d,J=8.0Hz,1H), 8.06(m,2H), 7.82(dd,J=8.0Hz ,J=2.0Hz,1H), 7.65(m,4H), 7.54(m,3H), 7.39(m,9H), 7.30(m,2H), 6.49( s,2H), 4.07(s,2H), 2.63(m,4H), 2.33(bs,3H), 2.06(m,4H), 1,40(s,9H).

[0283] Synthesis of compound PLC-32 [ka]

[0284] Compound PLC-32.1 General procedure for compound PLC-32.1: Ex-4.3 (6.3 g, 17.159 mmol, 1 equiv.) was suspended in 35 mL of anhydrous DMSO, and glycine (2.31 g, 30.77 mmol, 1.8 equiv.) was added to the reaction mixture at room temperature. The resulting mixture was stirred at 130 °C for 1 h (the mixture did not dissolve), and then heated to 160 °C for 1 h; LMCMS indicated 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 give 6.5 g of a greenish-yellow solid (90% yield). 1 H 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=8.7H) z,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).

[0285] Compound PLC-32.2 General procedure for compound PLC-32.2: PLC-32.1 (4.24 g, 10.0 mmol, 1 equiv.) was suspended in 2-MeTHF (150 mL) and HO (5.0 mL), and 4-(tert-butyl)benzeneboronic acid (3.56 g, 20 mmol, 2 equiv.), KCO (2.76 g, 20 mmol, 2 equiv.), and Pd(dppf)Cl (DCM) (163.3 mg, 0.2 mmol, 0.02 equiv.) were added. The reaction mixture was degassed three times using a Vac-Fill argon cycle and heated and stirred at 95 °C under an argon atmosphere for 12 h. 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 (85% yield). MS (APCI): C 20 H 10 Calculated for BrNO5 (MH) = 423; Found: 423. 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,2 H), 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).

[0286] Compound PLC-32 General procedure for compound PLC-32: PLC-32.2 (71.62 mg, 0.15 mmol, 1.5 equiv.) was suspended in anhydrous DCM (10.0 ml). To the mixture was added PLC-2.1 (58.5 mg, 0.1 mmol, 1 equiv.), DMAP-pTSA (58.8 mg, 0.2 mmol, 2 equiv.), and EDC·HCl (57.5 mg, 0.3 mmol, 3 equiv.). The mixture was then stirred at room temperature under argon for 5 hours, diluted with DCM (150 ml), filtered, and the solid was washed with 50 ml of DCM. The filtrate was collected and loaded onto an 80 g SiO column. The column was eluted with Hex-DCM (1 / 1), DCM alone, and then 0.5% EA in DCM. The good fractions were concentrated and washed with MeOH to give 80 mg (96% yield). MS (APCI): C 63 H 46 Calculated for BCl2F2N3O5 (M-) = 1044; Found: 1044. 1H NMR(400MHz,d2-TCE) δ 8.63(d,J=7.9Hz,1H), 8.58(d,J=8.3Hz,1H), 8.20(d,J=2.1Hz,1H), 8.01(d,J=8.1Hz,1H), 7.98~ 7.91(m,2H), 7.73(dd,J=8.7,2.1Hz,1H), 7.59~7.51(m,2H), 7.49~7.44(m,2H), 7.42(d,J=8.6Hz ,1H), 7.38(s,2H), 7.32(d,J=8.3Hz,1H), 7.27(dt,J=7.3,3.7Hz,4H), 7.20(dt,J=5.1,3.7Hz,2H ), 6.35(s,2H), 5.18(s,2H), 2.54(t,J=6.7Hz,4H), 2.22(s,4H), 1.99~1.90(m,4H), 1.31(s,10H).

[0287] Synthesis procedure for compound PLC-33 [ka]

[0288] Compound PLC-33.1 General procedure for compound PLC-33.1: PLC-32.1 (7.0 g, 16.50 mmol, 1 equiv.) was suspended in 2-MeTHF (150 mL) and 4-(trifluoromethyl)benzeneboronic acid (5.648 g, 29.7 mmol, 1.8 equiv.), K2CO3 (4.65 g, 33 mmol, 2 equiv.), HO (15 mL), and Pd(dppf)Cl2DCM (269.5 mg, 0.33 mmol, 0.02 equiv.) were added. After three vac-fill cycles of argon, the resulting mixture was heated and stirred at 95 °C under an argon atmosphere for 12 h. The mixture was cooled to room temperature and stirred with 1 N HCl (20 mL) for 15 min, then held at room temperature for 1 h. 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 give 6.70 g of a greenish-yellow solid, which was used in the next step without further purification (83% yield). MS (APCI): C 27 H 14Calculated for F3NO5 (M-) = 489; Found: 489. 1 H 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).

[0289] Compound PLC-33 General procedure for compound PLC-33: PLC-33.1 (73.4 mg, 0.15 mmol, 1.5 equiv.) was suspended in anhydrous DCM (10.0 mL) and PLC-2.1 (58.5 mg, 0.1 mmol, 1 equiv.), DMAP-pTSA (58.8 mg, 0.2 mmol, 2 equiv.), and EDC·HCl (57.5 mg, 0.3 mmol, 3 equiv.) were added. The mixture was stirred under argon for 5 hours at room temperature, diluted with DCM (150 mL), filtered, and the solid was washed with 50 mL of DCM. The filtrate was collected and loaded onto an 80 g SiO column. The column was eluted with Hex-DCM (1 / 1), DCM only, and then 0.5% EA in DCM. The pure fractions were collected, concentrated, and washed with hot MeOH to give 82 mg of a dark purple solid (77% yield). MS (APCI): Chemical Formula: C 60 H 37 Calculated for BCl2F5N3O5 (M-) = 1055; Found: 1055. 1 H NMR(400MHz,d2-TCE) δ 8.66(d,J=7.9Hz,1H), 8.61(d,J=8.4Hz,1H), 8.21(d,J=2.2Hz,1H), 8.04(d,J= 8.1Hz,1H), 7.96(s,2H), 7.73(dd,J=9.7,1.8Hz,H), 7.47(d,J=8.6Hz,1H), 7.38 (s,1H), 7.35(d,J=8.4Hz,1H), 7.27(dt,J=7.3,3.7Hz,3H), 7.23~7.16(m,2H), 6 .35(s,2H), 5.19(s,2H), 2.53(d,J=7.4Hz,4H), 2.22(s,4H), 2.03~1.86(m,4H).

[0290] Synthesis procedure for PLC-34 [ka]

[0291] General procedure for compound PLC-34.1: Ex-4.3 (1.223 g, 3.33 mmol, 1 equiv.) was suspended in 35 mL of anhydrous DMSO, and 5-amino-1-pentanol (0.687 g, 6.66 mmol, 2 equiv.) was added to the reaction mixture at room temperature. The resulting mixture was stirred at 160 °C for 45 min, and LMCMS indicated the reaction was complete. After cooling to room temperature, the solid product was filtered, washed with water (250 mL), then MeOH (100 mL), and dried in a vacuum oven to give 1.2 g of a greenish-yellow solid (85% yield). MS (APCI): C 23 H 18 Calculated for BrNO4 (M-) = 453; Found: 453. 1 H NMR(400MHz,d2-TCE) δ 8.52(d,J=7.8Hz,1H), 8.48(d,J=8.3Hz,1H), 8.09(d,J=2.3Hz,1H), 7.82(d,J=8.0Hz,1H), 7.54(dd,J=8.8,2.3Hz,1H), 7.23(d,J=8.3Hz,1H) ), 7.19(d,J=8.8Hz,1H), 4.14~4.02(m,2H), 3.64~3.49(m,2H), 1.68(p,J=7.7Hz,2H), 1.60~1.54(m,2H), 1.41(q,J=8.0Hz,2H), 1.28(s,1H).

[0292] General procedure for compound PLC-34.2: PLC-34.1 (1.13 g, 2.5 mmol, 1 equiv.) was suspended in DMF (10 ml), HO (5 ml), and 4-(trifluoromethyl)benzeneboronic acid (0.949 g, 5.0 mmol, 2 equiv.), KCO (0.691 g, 5.0 mmol, 2 equiv.), and Pd(dppf)Cl DCM (40.8 mg, 0.05 mmol, 0.02 equiv.) were added. The mixture was degassed three times with a Vac-Fill argon cycle and heated and stirred at 90 °C for 5 h. The reaction mixture was cooled to room temperature, and water was added. The resulting mixture was kept at room temperature for 12 h. The greenish-yellow solid was filtered and washed with water and then MeOH to give 1.24 g of a greenish-yellow solid (95% yield). MS (APCI): C 30 H 22 Calculated for F3NO4 (M-) = 517; Found: 517. 1 H NMR (400MHz, d2-TCE) 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=8.3Hz,1H), 4.09(t,J=7.5Hz,2H), 3.57(q,J=6.2Hz,2H), 1.69(p,J=7 .8Hz,2H), 1.61~1.54(m,2H), 1.42(q,J=8.0Hz,2H), 1.28(t,J=5.5Hz,1H).

[0293] General procedure for compound PLC-34.3: A mixture of PLC-34.2 (0.66 g, 1.288 mmol) and 48% aqueous HBr (20.0 ml) was refluxed in a heat block with stirring at 120° C. for 5 hours (48% HBr, boiling point: 126° C.). After cooling to room temperature, the mixture was poured into ice water, and the solid was filtered, washed with water, and dried in a vacuum oven to give 82% of the desired compound, containing unreacted SM. 0.7 g of a greenish-yellow solid (93% yield) was obtained. The product was used in the next step without further purification. MS (APCI): C 30 H 21Calculated for BrF3NO3 (M-) = 581; Found: 581. 1 H NMR(400MHz,d2-TCE) 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=8.3Hz,1H), 4.09(t,J=7.5Hz,3H), 3.38(t,J=6.7Hz,2H), 1.97~1.81(m,2H), 1.69(t,J=7.8Hz,2H).

[0294] Compound PLC-34 General procedure for compound PLC-34: PLC-34.3 (87.06 mg, 0.15 mmol, 1.5 equiv.) was suspended in anhydrous DMF (10.0 mL) and PLC-2.1 (63.65 mg, 0.10 mmol, 1 equiv.), KCO (41.46 mg, 0.3 mmol, 2 equiv.), and NaI (8.3 mg, catalytic amount) were added. The resulting mixture was stirred at 65 °C under argon for 15 hours, cooled to room temperature, filtered, and washed with 50 mL of water. The crude product was loaded onto a 40 g silica gel column and eluted with Hex:DCM (9:1) to DCM to give 75 mg of a reddish-brown solid (69% yield). MS (APCI): C 63 H 45 Calculated for BCl2F5N3O4 (M-) = 1083; Found: 1083. 1H NMR(400MHz,d2-TCE) δ 8.59(d,J=7.9Hz,1H), 8.54(d,J=8.3Hz,1H), 8.18(d,J=2.1Hz,1H), 8.00(d,J=8.1Hz,1H), 7.96 (s,1H), 7.70(dd,J=7.4,2.2Hz,3H), 7.43(d,J=8.6Hz,1H), 7.30(d,J=8.3Hz,1H), 7.29~7.25(m ,2H), 7.22~7.19(m,1H), 6.98(s,2H), 6.39(s,2H), 4.15(t,J=7.5Hz,2H), 3.99(t,J=6.2Hz,2H) , 2.55(t,J=6.6Hz,2H), 2.23(s,2H), 1.98~1.92(m,2H), 1.86(s,1H), 1.77(s,1H), 1.58(s,2H).

[0295] Synthesis procedure for PLC-35 [ka]

[0296] General procedure for compound PLC-35.1-9-bromo-2-(2-(2-hydroxyethoxy)ethyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione: A 100 mL flask was equipped with a stir bar. To the flask was added Ex-4.3 (1.5 g, 4.1 mmol), 2-(2-aminoethoxy)ethanol-1-ol (859.0 mg, 8.2 mmol), and DMAP (35.1 mg, 0.3 mmol) in DMF (30 mL) and degassed at room temperature. The reaction mixture was heated to 165° C. and maintained at this temperature for 2 hours. TLC and LCMS indicated completion of the reaction. The reaction was cooled to room temperature. HO (70 mL) was added to precipitate the product. The precipitate was collected by filtration. The solid was washed with HO (150 ml) and further dried in a vacuum oven at 100 °C for 3 h to give PLC-35.1 (1.45 g, 78% yield) as a yellow solid for the next step without further purification. MS (APCI): C 22 H 16 Calculated value for BrNO5 ([MH] - )=454 Actual value: 454.1 H NMR(400MHz,CDCl2CDCl2) 8.62(d,J=8.0Hz,1H), 8.59(d,J=8.0Hz,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).

[0297] General procedure for compound PLC-35.2-2-(2-(2-hydroxyethoxy)ethyl)-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione: A 250 mL flask was equipped with a stir bar. To the flask was added PLC-35.1 (800.0 mg, 1.8 mmol), 4-(trifluoromethyl)phenylboronic acid (670.0 mg, 3.5 mmol), Pd(dppf)Cl (90.6 mg, 0.1 mmol), and KCO (659.5 mg, 4.8 mmol) in THF / DMF / HO (48 mL / 9.6 mL / 4.8 mL) and degassed at room temperature. The reaction mixture was heated to 80 °C and maintained at this temperature overnight. The reaction was monitored using TLC. Upon completion, the reaction was worked up by the addition of HO (150 ml), which was added to precipitate the product. The precipitate was collected by filtration. The solid was washed with HO (200 ml) and MeOH (20 ml) and further dried in a vacuum oven at 100° C. for 3 hours to give PLC-35.2 as a yellow-green solid (quantitative yield) for the next step without further purification. MS (APCI): C 29 H 20 Calculated value for F3NO5 ([M+H] + )=520 Actual value: 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).

[0298] General procedure for compounds PLC-35.3A and PLC-35.3B—2-(2-(1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)ethoxy)ethyl methanesulfonate and 2-(2-(2-chloroethoxy)ethyl)-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione: A 100 mL flask was equipped with a stir bar. To the flask was added PLC-35.2 (900.0 mg, 1.7 mmol) and DMF / THF (18 mL / 6 mL). 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. Upon completion, the reaction was worked up by the addition of HO (150 mL), which was added to precipitate the product. The precipitate was collected by filtration. The solid was washed with HO (100 mL) and MeOH (15 mL) and further dried in a vacuum oven at 100° C. for 3 hours to afford a mixture of PLC-35.3A and PLC-35.3B (approximately 1:1 molar ratio) as a yellow solid for the next step without further purification (quantitative yield). For PLC-35.3A, MS (APCI): C 30 H 22 F3NO7S([M+H] + ) Calculated value = 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). PLC-35.3B case, MS (APCI): C 29 H 19 ClF3NO4([MH) - ) Calculated value = 537 Measured value: 537. 1 H 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=8.4H z,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).

[0299] General procedure for compound PLC-35.4-2,6-dichloro-4-(2-(2-(1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)ethoxy)ethoxy)benzaldehyde: To a 100 mL flask was added NaH (69.1 mg, 2.9 mmol) and DMF (20 mL), followed by 4-hydroxy-2,6-dichlorobenzaldehyde (413.3 mg, 2.2 mmol). The mixture was allowed to stir at room temperature for 10 minutes. A mixture of PLC-35.3A (0.7 mmol) and PLC-35.3B (0.7 mmol) (total 862.0 mg, 1.4 mmol) was added. The reaction was heated to 160° C. and allowed to stir at this temperature overnight. TLC (50% EtOAc in hexanes) showed the reaction was complete. The reaction mixture was purified by silica gel flash chromatography using EtOAc in DCM (0% to 40%) as the eluent to give pure compound PLC-35.4 (580.0 mg, 60% yield) as a yellow solid. MS (APCI): C 36 H 22 Calculated value for Cl2F3NO6 ([MH] - )=691 Actual value: 691. 1 H NMR(400MHz,CDCl2CDCl2) δ 10.06(s,1H), 8.60(d,J=8.0Hz,1H), 8.57(d,J=8.0Hz,1H), 8.24(d,J=2.0Hz,1H), 8.02(d,J=8.0Hz,1H), 7.81(m,5H), 7.52( d,J=8.0Hz,1H), 7.34(d,J=8.0Hz,1H), 6.56(s,2H), 4.44(t,J=2.0Hz,2H), 3.98(m,2H), 3.93(t,J=2.0Hz,2H), 3.86(m,2H).

[0300] General procedure for compound PLC-35-2-(2-(2-(3,5-dichloro-4-(19,19-difluoro-6,7,11,12,13,19-hexahydro-5H-18|4,19|4-benzo[3',4']cyclohepta[1',2':4,5]pyrrolo[1,2-c]benzo[3',4']cyclohepta[1',2':4,5]pyrrolo[2,1-f][1,3,2]diazaborin-9-yl)phenoxy)ethoxy)ethyl)-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione): A 100 mL two-neck round-bottom flask was equipped with an air condenser and a stir bar. To a flask were added PLC-35.4 (140.0 mg, 0.2 mmol) and Ex-7.3 (77.7 mg, 0.4 mmol), followed by anhydrous dichloromethane (4 mL). The reaction mixture was sparged with Ar for 30 minutes, and then p-TsOH·HO (1.2 mg, 0.01 mmol) was added. The reaction solution was maintained at this temperature for 2 hours. DDQ (25.0 mg, 0.1 mmol) was then added. The reaction was maintained at room temperature for 30 minutes. BF·OEt (0.3 mL, 2.4 mmol) and EtN (0.2 mL, 1.6 mmol) were then added at room temperature. The reaction mixture was maintained at room temperature overnight. The reaction mixture was loaded onto silica gel and purified by flash chromatography using EtOAc in DCM (0→5%) as the eluent to give pure PLC-35 as a dark purple solid (121.0 mg, 55% yield). MS (APCI): C 62 H 43 Calculated value for BCl2F5N3O5 ([MH] - )=1086 Actual value: 1086. 1H NMR(400MHz,CDCl2CDCl2) 8.69(d,J=8.0Hz,1H), 8.63(d,J=8.0Hz,1H), 8.26(d,J=2.4Hz,1H), 8.08(d,J=8.0Hz,1H), 8.04(m,2H), 7.78(m,5) H), 7.51(d,J=8.0Hz,1H), 7.34(m,7H), 6.99(s,2H), 6.44(s,2H), 4.49(t,J=2.0Hz,2H), 4.18(m,2H), 3.96(m,4H), 2.63(m,4H), 2.31(bs,4H), 2.04(m,4H).

[0301] Synthesis procedure for compound PLC-36 [ka]

[0302] General procedure for compound PLC-36.5-(2-(4-(9-bromo-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid): A 100 mL two-neck 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 Ex-4.3 (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). The reaction mixture was stirred under argon and the heat block was set to 170 °C. The reaction mixture was stirred at 170 °C for 9 h, 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 by suction for 5 minutes. The wet precipitate was dried overnight in a vacuum oven at about 110°C. 366 mg (107% yield) of a yellowish powder was obtained. NMR indicates about 10%-15% of the dimethylamide by-product. MS (APCI): C 26 H 14 Calculated for BrNO5 (M+H) = 500; Found: 500. 1H NMR(400MHz,DMSO-d6) δ 8.60(d,J=2.3Hz,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).

[0303] General procedure for compound PLC-36. 2-(2-(4-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane): A 250 mL two-neck 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 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 KCO (11.0 mmol, 1.520 g). The reaction mixture was stirred at room temperature under an argon atmosphere for 5 minutes, then the heat block was set to 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 NaHCO3 (50 mL), brine (50 mL), dried over MgSO4, filtered, and evaporated to dryness in vacuo. A pale yellow oil (4.166 g, 114% yield) was obtained. NMR indicated it was a mixture of the desired product and the starting bromoglycol (approximately 57% product estimated). This was used in the next step without further purification. MS (APCI): C 19 H 31 Calculated for BO6 (M+H)=367; Found: 367. 1H NMR (400MHz, methanol-d4) δ 7.69~7.63(m,2H), 6.95~6.90(m,2H), 4.18~4.11(m,2H), 3.86~3.82(m,2 H), 3.72~3.67(m,2H), 3.66~3.60(m,2H), 3.54~3.48(m,4H), 3.34(s,3H).

[0304] General procedure for compound PLC-36.3-(2-(4-(9-(4-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid): A 250 mL, two-neck 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 and a flow control valve. The system was flushed with argon. To a flask was added PLC-36.1 (2.00 mmol, 1001 mg), PLC-36.2 (4.00 mmol, 1465 mg), K2CO3 (5.50 mmol, 760 mg), and Pd(dppf)Cl2 (0.140 mmol, 102 mg), 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 to 80 °C for 2 hours. The reaction mixture was quenched with 6 N 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 × 50 mL). The combined organic layers were washed with brine (50 mL), dried over MgSO4, filtered, and evaporated to dryness in vacuo (with DMF). The crude product was evaporated onto approximately 50 g of flash silica gel and placed on a loader. Purification was carried out by flash chromatography on silica gel (220 g, solids, equilibration 100% DCM, elution 100% DCM (2 CV) → 40% (EtOAc / 0.1% TFA) / DCM (20 CV) → 70% (EtOAc / 0.1% TFA) / DCM (20 CV)). The product-containing fractions were evaporated to dryness in vacuo. 722 mg (55% yield) of a yellow solid was obtained. MS (APCI): C 39 H33 Calculated value of NO9についての(M+H)=660; Measured value: 660. 1 H 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,1 H), 7.84~7.78(m,2H), 7.55(d,J=8.7Hz,1H), 7.48(d,J=8.3Hz,1H), 7.41(d,J=8.1H z,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).

[0305] General procedure for compound PLC-36-(3,5-dichloro-4-(19,19-difluoro-6,7,11,12,13,19-hexahydro-5H-18|4,19|4-benzo[3',4']cyclohepta[1',2':4,5]pyrrolo[1,2-c]benzo[3',4']cyclohepta[1',2':4,5]pyrrolo[2,1-f][1,3,2]diazaborin-9-yl)phenyl 2-(4-(9-(4-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate): Place a 40 mL vial containing 10 mL of PLC-36-(3,5-dichloro-4-(19,19-difluoro-6,7,11,12,13,19-hexahydro-5H-18|4,19|4-benzo[3',4']cyclohepta[1',2':4,5]pyrrolo[2,1-f][1,3,2]diazaborin-9-yl)phenyl 2-(4-(9-(4-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)phenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetate) in a 40 mL vial with a stir bar. The vial was charged with PLC-2.1, followed by 3,5-dichloro-4-(19,19-difluoro-6,7,11,12,13,19-hexahydro-5H-18|4,19|4-benzo[3',4']cyclohepta[1',2':4,5]pyrrolo[1,2-c]benzo[3',4']cyclohepta[1',2':4,5]pyrrolo[2,1-f][1,3,2]diazaborin-9-yl)phenol (0.050 mmol, 29.3 mg), PLC-36.3 (0.075 mmol, 49.5 mg), DMAP·pTsOH salt (0.100 mmol, 29.4 mg), and EDC·HCl (0.300 mmol, 29 mg), 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. Purification was achieved by flash chromatography on silica gel (120 g, solids, equilibrated with 100% DCM, eluting with 100% DCM (3 CV) → 5.8% EtOAc / DCM (11.6 CV) → 13.3% EtOAc / DCM (6.0 CV) → 50% EtOAc / DCM (10 CV)). Fractions containing the product were evaporated to dryness in vacuo. The crude product was triturated with hot methanol. The product was filtered off, sucked dry, and then dried in a vacuum oven at approximately 110°C. A dark red solid, 47.1 mg (77% yield) was obtained. MS (APCI): C 72 H 56 Calculated for BCl2F2N3O9 (M-) = 1225; Found: 1225. 1H NMR (400MHz, Tactron-d2) δ 8.68(d,J=7.8Hz,1H), 8.63(d,J=8.3Hz,1H), 8.25(d,J=2.1Hz,1H), 8.11(d,J=8.1Hz,1H), 8.09~8.00(m,2H) , 7.78(dd,J=8.6,2.1Hz,1H), 7.69~7.61(m,4H), 7.50(d,J=8.6Hz,1H), 7.46~7.34(m,9H), 7.33~7.26(m,2H), 7.14~7.05(m,2H), 6.48(s,2H), 4.22(t,J=4.7Hz,2H), 4.07(s,2H), 3.94~3.88(m,2H), 3.78~3.72(m,2H), 3. 72~3.62(m,4H), 3.59~3.53(m,2H), 3.38(s,3H), 2.64(t,J=6.8Hz,4H), 2.44~2.22(m,4H), 2.12~1.97(m,4H).

[0306] Synthesis instructions for compound PLC-37

change

[0307] General procedure for compound PLC-37.1-(9-bromo-2-(2-hydroxyethyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione): A 50 mL two-neck 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. To the flask was added Ex-4.3 (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 to 165 °C. The reaction mixture was stirred at this temperature for 3 h, 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 a few minutes, then stirred at room temperature for 30 minutes, and the solid product was then filtered off and washed with water. The crude filter cake was dried overnight in a vacuum oven at about 110°C. 1.038 g (84% yield) of a dark brownish solid was obtained. MS (APCI): C 20 H 12 Calculated for BrNO4 (M+H) = 410; Found: 410.

[0308] General procedure for compound PLC-37.2-(2-(2-hydroxyethyl)-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione): PLC-39.2 was synthesized in a manner similar to that for PLC-36.7 from PLC-37.1 (2.531 mmol, 1.038 g), (4-(trifluoromethyl)phenyl)boronic acid (5.062 mmol, 961 mg), KCO (6.960 mmol, 962 mg), and Pd(dppf)Cl (0.177 mmol, 130 mg) in THF / DMF / HO (60 mL / 12 mL / 6 mL) at 80 °C for 30 minutes. 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 overnight in a vacuum oven at about 110° C. 1.017 g (84% yield) was obtained. MS (APCI): C 27 H 16 Calculated for F3NO4 (M+H) = 476; Found: 476. 1 H 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), 7.83~7.75(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).

[0309] General procedure for compound PLC-37.3-(2-(2-chloroethyl)-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione): A 250 mL two-neck 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. To the flask was added PLC-37.2 (2.124 mmol, 1.01 g), pTsCl (6.372 mmol, 1.215 g), anhydrous DMF (20 mL), and EtN (6.372 mmol, 0.888 mL). The reaction mixture was stirred under argon and heated to 80 °C for 2 h. An unexpected reaction occurred when the tosylate was replaced in situ by chloride ion. 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 overnight in a vacuum oven at about 110° C. 974 mg of an orange solid (93% yield) was obtained. MS (APCI): C 27 H 15 Calculated for ClF3NO3 (M+H) = 494; Found: 494. 1 H 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), 7.86~7.7 3(m,5H), 7.53(d,J=8.6Hz,1H), 7.39(d,J=8.4Hz,1H), 4.56(t,J=6.9Hz,2H), 3.87(t,J=6.8Hz,2H).

[0310] General procedure for compound PLC-37.4-(2,6-dichloro-4-(2-(1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)ethoxy)benzaldehyde): A 100 mL two-neck 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. To the flask was added NaH (60% in mineral oil) (1.214 mmol, 29.1 mg, 60%, 49 mg), followed by anhydrous DMF (20 mL). To the flask was added 2,6-dichloro-4-hydroxybenzaldehyde (1.821 mmol, 348 mg). The reaction mixture was stirred under argon and the heat block was set to 50 °C. The reaction was stirred at 50°C for 5 minutes, then PLC-37.3 (0.607 mmol, 300 mg) was added. The flask was stoppered and stirred under argon. The temperature of the heat block was increased to 160°C. The reaction mixture was stirred at 160°C for 90 minutes, then at room temperature overnight. Water (100 mL) was added to triturate the crude product, which was filtered off and washed with water. The crude product was dissolved in DCM and evaporated to dryness in vacuo. The crude product was evaporated to dryness in vacuo onto flash silica gel (approximately 20 g). Purification was carried out by flash chromatography on silica gel (120 g, solids, equilibrated 100% DCM / hexanes, eluted 100% DCM / hexanes (7 CV) → 0% EtOAc / DCM (0 CV) → 0% EtOAc / DCM (5 CV) → 40% EtOAc / DCM (40 CV)). Fractions containing the product were evaporated to dryness in vacuo. 152 mg (39% yield) of a yellow solid was obtained. MS(APCI):C 34 H 18 Calculated for Cl2F3NO5 (M-) = 647; Found: 647. 1H NMR(400MHz,TCE) δ 10.36(s,1H), 8.68(d,J=7.9Hz,1H), 8.63(d,J=8.3Hz,1H), 8.26(d,J=2.1Hz,1H), 8.07(d,J=8.0Hz,1H), 7.85~7.72(m,5 H), 7.52(d,J=8.6Hz,1H), 7.39(d,J=8.4Hz,1H), 6.99(s,2H), 6.93(s,1H), 4.65(t,J=6.1Hz,2H), 4.40(t,J=6.1Hz,2H).

[0311] Compound PLC-37 General procedure for compound PLC-37-(2-(2-(3,5-dichloro-4-(19,19-difluoro-6,7,11,12,13,19-hexahydro-5H-18|4,19|4-benzo[3′,4′]cyclohepta[1′,2′:4,5]pyrrolo[1,2-c]benzo[3′,4′]cyclohepta[1′,2′:4,5]pyrrolo[2,1-f][1,3,2]diazaborin-9-yl)phenoxy)ethyl)-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione): A 100 mL two-neck round-bottom flask was placed in an aluminum heat block and a stir bar was added. The flask was fitted with a finned condenser / gas adapter, a stopper, and a flow control valve. The system was flushed with argon. PLC-37.4 (0.075 mmol, 49 mg) and Ex-7.3-1,4,5,6-tetrahydrobenzo[6,7]cyclohepta[1,2-b]pyrrole (0.1575 mmol, 29 mg) were added to the flask, followed by anhydrous DCM (20 mL). Under an argon atmosphere, the reaction mixture was sparged with nitrogen for 10 minutes. A few small granules of pTsOH·HO were collected on the end of a spatula and immersed in 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 at room temperature for 1 hour, at which point TLC indicated complete conversion to the desired dipyrromethane. DDQ (0.1275 mmol, 29 mg) was added to the flask, and the reaction mixture was stirred at room temperature for 15 minutes. TLC showed complete oxidation to the dipyrromethene. To this flask was added EtN (0.600 mmol, 0.084 mL) and BF OEt (0.900 mmol, 0.111 mL). The addition of both reagents was repeated after 2 min, then the heat block was set to 50 °C, and the reaction mixture was stirred at this temperature for 2 h under argon. The crude BODIPY was loaded directly onto flash silica gel (25 g). Purification was performed by flash chromatography on silica gel (80 g, solids, equilibrated 80% DCM / hexane, eluted 80% DCM / hexane (2 CV) → 100% DCM / hexane (5 CV) → isocratic 100% DCM / hexane (approximately 25 CV) → 100% DCM / hexane / 0.5% EtOAc (approximately 10 CV)).The product elutes as a broad peak. Fractions containing the product were evaporated to dryness in vacuo. 89 mg (quantitative yield) of a dark red solid was obtained. MS (APCI): C. 60 H 39 Calculated for BCl2F5N3O4 (M-) = 1041; Found: 1041. 1 H NMR(400MHz,TCE) δ 8.72(d,J=7.9Hz,1H), 8.67(d,J=8.4Hz,1H), 8.27(d,J=2.2Hz,1H), 8.10(d,J=8.1Hz ,1H), 8.04(dd,J=5.8,3.5Hz,2H), 7.84~7.75(m,5H), 7.53(d,J=8.6Hz,1H), 7.41(d,J =8.3Hz,1H), 7.39~7.32(m,4H), 7.32~7.25(m,2H), 7.14(s,2H), 4.70(t,J=6.2Hz,2H ), 4.42(t,J=6.2Hz,2H), 2.62(t,J=7.0Hz,4H), 2.41~2.18(m,4H), 2.11~1.93(m,4H).

[0312] Synthesis procedure for PLC-38 [ka]

[0313] Synthesis of PLC-38.1 (9-bromo-2-(3-hydroxypropyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione): Ex-4.3 (1.223 g, 3.33 mmol, 1 equiv.) was suspended in 35 mL of anhydrous DMSO, and 3-amino-1-propanol (1.5 g, 20.0 mmol, 6 equiv.) was added to the reaction mixture at room temperature. The resulting mixture was stirred at 160 °C for 45 minutes, and LCMS showed the reaction was complete. After cooling to room temperature, the solid product was filtered, washed with water (250 mL) and then MeOH (100 mL), and dried in a vacuum oven to give 1.2 g of a greenish-yellow solid (92% yield). MS (APCI): C 23 H 18 Calculated for BrNO4 (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=8.8Hz,1H), 4.24(t,J=6.1Hz,2H), 3.48(q,J=6.1Hz,2H), 3.06(t,J=6.9Hz,1H), 1.95~1.83(m,2H).

[0314] Synthesis of PLC-38.2 (2-(3-hydroxypropyl)-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione): PLC-38.1 (1.06 g, 2.5 mmol, 1 equiv.) was suspended in DMF (10 mL) and HO (5 mL), and 4-(trifluoromethyl)benzeneboronic acid (0.949 g, 5.0 mmol, 2 equiv.), KCO (0.691 g, 5.0 mmol, 2 equiv.), and Pd(dppf)Cl·DCM (40.8 mg, 0.05 mmol, 0.02 equiv.) were added. The mixture was degassed three times with a Vac-Fill argon cycle and heated and stirred at 90 °C for 5 h. The reaction mixture was cooled to room temperature, and water was added. The resulting mixture was kept at room temperature for 12 h. 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): C 30 H 22 Calculated for F3NO4 (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=8.3Hz,1H), 4.09(t,J=7.5Hz,2H), 3.57(q,J=6.2Hz,2H), 1.69(p,J=7 .8Hz,2H), 1.61~1.54(m,2H), 1.42(q,J=8.0Hz,2H), 1.28(t,J=5.5Hz,1H).

[0315] Synthesis of PLC-38.3 (2-(3-bromopropyl)-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione): A mixture of PLC-38.2 (1.6 g, 3.2 mmol) and 48% aqueous HBr (30.0 ml) was heated to reflux with stirring at 130° C. in a heat block for 3 days. The same amount of 48% aqueous HBr was added twice more over the next 2 days, for a total volume of 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 give 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): C 30 H 21 Calculated for BrF3NO3 (M-) = 551; Found: 551. 1 H 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=8.0Hz,1H), 7.70(s,5H), 7.41 (d,J=8.6Hz,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).

[0316] PLC-38 (2-(3-(3,5-dichloro-4-(19,19-difluoro-6,7,11,12,13,19-hexahydro-5H-18|4,19|4-benzo[3',4']cyclohepta[1',2':4,5]pyrrolo[1,2c]benzo[3',4']cyclohepta[1',2':4,5]pyrrolo[2,1-f][1,3,2]diazaborin-9-yl)phenoxy)propyl)-9-(4-(trifluoromethyl)-2-(2-(3-(3,5-dichloro-4-(19,19-difluoro-6,7,11,12,13,19-hexahydro-5H-18|4,19|4- ... Synthesis of (trimethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione: PLC-38.3 (41.425 mg, 0.075 mmol, 1.15 equiv.) was suspended in anhydrous DMF (2.0 mL) and PLC-2.1 (38.04 mg, 0.065 mmol, 1 equiv.), KCO (0.73 mg, 0.15 mmol, 2.3 equiv.), and NaI (4.15 mg) were added. The resulting mixture was stirred at 85 °C under argon for 16 h, cooled to room temperature, filtered, and washed with 50 mL of water. The crude product was loaded onto a 40 g silica gel column and eluted with Hex:DCM (9:1) to DCM to give 49 mg of a dark purple solid (71% yield). MS (APCI): C 63 H 45 Calculated for BCl2F5N3O4 (M-) = 1055; Found: 1055. 1 H NMR(400MHz,) δ 8.60(d,J=7.8Hz,1H), 8.55(d,J=8.3Hz,1H), 8.18(d,J=2.2Hz,1H), 8.00(d,J=8.1Hz,1 H), 7.95(d,J=5.9Hz,2H), 7.74~7.65(m,4H), 7.44(d,J=8.6Hz,1H), 7.34~7.24(m,4H), 7.24~7.14(m,2H), 6.91(s,2H), 6.38(s,2H), 4.36(t,J=6.9Hz,2H), 4.13(t,J=6.1Hz,2 H), 2.54(t,J=6.7Hz,4H), 2.28~2.19(m,4H), 2.06~1.85(m,4H), 0.78(d,J=14.2Hz,2H).

[0317] Synthesis procedure for PLC-39 [ka]

[0318] Compound 39.1: A mixture of compound Ex-4.4 (649 mg, 1.23 mmol), 4-(trifluoromethyl)phenylboronic acid (467 mg, 2.46 mmol), Pd(dppf)Cl (45 mg, 0.06 mmol), and potassium carbonate (345 mg, 2.5 mmol) in a cosolvent of THF / DMF / water (30 mL / 6 mL / 3 mL) was degassed and then heated at 80 °C overnight. The mixture was worked up with 300 mL of ethyl acetate and 50 mL of 0.6 N aqueous hydrochloric acid. The aqueous phase was extracted with ethyl acetate (150 mL × 3). The organic phase was collected, washed with brine (100 mL × 2), dried over sodium sulfate, and then dry-loaded onto silica gel and purified by flash chromatography using an eluent of DCM / EA (0% → 80% EA with 0.1% TFA). The main desired fraction was collected and the solvent removed under reduced pressure to give a yellow solid (414 mg, 57% yield). 1H NMR(400MHz,d2-TCE) δ 8.55(dd,J=18.1,8.1Hz,2H), 8.16(d,J=2.2Hz,1H), 8.00(d,J=8.1Hz,1H), 7.68(dd,J=8.6,2.1Hz,1H), 7.66~7.59(m,2H), 7.43(d ,J=8.6Hz,1H), 7.32(tt,J=8.2,4.2Hz,5H), 7.20~7.13(m,2H), 2.72(t,J=7.6Hz,2H), 2.39(t,J=7.3Hz,2H), 1.99(q,J=7.4Hz,2H).

[0319] Compound PLC-39: A mixture of PLC-1.3 (32 mg, 0.0547 mmol), PLC-39.1 (48.7 mg, 0.082 mmol), EDC·HCl (60 mg, 0.31 mmol), and DMAP / p-TsOH (15 mg, 0.05 mmol) in DCM (5 mL) was stirred overnight at room temperature. The resulting mixture was then loaded onto silica gel and purified by flash chromatography using an eluent of DCM / ethyl acetate (0% → 10% ethyl acetate). The main red fraction was collected and concentrated under reduced pressure to 0.5 mL, followed by the addition of 10 mL of methanol. The resulting precipitate was filtered and dried in air to give a dark red solid (44 mg, 69% yield). H NMR (400 MHz, d2-TCE) δ 8.56(dd,J=17.8,8.1Hz,2H), 8.16(d,J=2.2Hz,1H), 7.99(dd,J=19.8,6.8Hz,3H), 7.68(d d,J=8.6,2.1Hz,1H), 7.66~7.59(m,2H), 7.44(d,J=8.6Hz,1H), 7.41~7.35(m,2H), 7.35~7. 25(m,9H), 7.22(dd,J=8.7,4.2Hz,4H), 6.40(s,2H), 2.82(t,J=7.5Hz,2H), 2.67(t,J=7.4 Hz,2H), 2.55(t,J=6.7Hz,4H), 2.24(bs,4H), 2.14(q,J=7.5Hz,2H), 1.96(t,J=7.1Hz,4H).

[0320] Synthesis procedure of PLC-40 [ka]

[0321] Compound 40.1: A mixture of 9-bromo-2-(3-hydroxypropyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione (PLC-38.1, 330 mg, 0.778 mmol), (2,4,6-triisopropylphenyl)boronic acid (290 mg, 1.17 mmol), Pd(PPh3)4 (80 mg, 0.069 mmol), and K2CO3 (320 mg, 2.32 mmol) in 1,4-dioxane / DMF / water (15 mL / 3 mL / 1.5 mL) was degassed and heated at 90 °C for 24 h. 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-): C 36 H 37 Calculated value for NO4 = 547.27; Actual value: 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), 2.65~2.43(m,2H), 1.89(d,J=6.2Hz,2H), 1.24(d,J=6.9Hz,6H), 1.03(t,J=7.1Hz,12H).

[0322] Compound 40.2: To a solution of compound PLC-40.1 (210 mg, 0.384 mmol) in 20 mL of DCM, carbon tetrabromide (CBr4, 252 mg, 0.76 mmol) and triphenylphosphine (203 mg, 0.77 mmol) were added at room temperature. The whole was stirred for 30 minutes. TLC showed that the reaction was complete. The mixture was loaded onto silica gel and purified by flash chromatography using an eluent of hexane / DCM (0% to 100% DCM). The desired fractions were collected and concentrated under reduced pressure to give a yellow solid (100 mg, 43% yield). LCMS (APCI+): C 36 H 37Calculated for BrNO3 (M+H): 610.19; found: 610. 1H NMR (400 MHz, d2-TCE) δ 8.52 (dd, J = 8.1, 2.5 Hz, 2H), 8.00–7.72 (m, 2H), 7.45–7.19 (m, 3H), 6.98 (s, 2H), 4.23 (t, J = 7.0 Hz, 2H), 3.44 (t, J = 6.8 Hz, 2H), 3.01–2.80 (m, 1H), 2.69–2.45 (m, 2H), 2.26 (q, J = 6.9 Hz, 2H), 1.24 (d, J = 6.9 Hz, 6H), 1.03 (t, J = 6.9 Hz, 12H).

[0323] Compound 40: A mixture of compound PLC-40.2 (50 mg, 0.082 mmol), PLC-1.3 (58.5 mg, 0.10 mmol), and K2CO3 (20.7 mg, 0.15 mmol) in anhydrous DMF was sonicated for 3 minutes and then heated at 75 °C under an argon atmosphere for 5 hours. 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, and then loaded onto silica gel and purified by flash chromatography using an eluent of DCM / EA (0% to 5% EA). The desired main fraction was collected, concentrated, triturated with methanol, and then filtered to give a dark red solid (70 mg, 76.6% yield). LCMS (APCI-): C 69 H 60 Calculated for BCl2F2N3O4: 1113.40; Found: 1113. 1H NMR (400 MHz, 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) ), 2.98~2.77(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).

[0324] Synthesis of compound PLC-41 [ka]

[0325] General procedure for the synthesis of compound PLC-41.1—9-bromo-2-(4-hydroxybutyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione: A 100 mL flask was equipped with a stir bar. Compound Ex-4.3 (1.0 g, 2.7 mmol), 4-aminobutan-1-ol (485.3 mg, 5.4 mmol), and DMAP (23.1 mg, 0.19 mmol) in DMF (20 mL) were added to the flask and degassed at room temperature. The reaction mixture was heated to 165° C. and maintained at this temperature for 2.5 hours. TLC and LCMS indicated the reaction was complete. The reaction was cooled to room temperature. HO (80 mL) was added. The solid product was collected by vacuum filtration, washed with HO (100 ml), and further dried in a vacuum oven at 100° C. for 3 hours to give PLC-41.1 (908.0 mg, 77% yield) as a brown solid for the next step without further purification. MS (APCI): Chemical Formula: C 22 H 16 Calculated for BrNO ([MH]) = 438. Found: 438. H NMR (400 MHz, CDClCDCl): 8.62 (d, J = 8.0 Hz, 1H), 8.58 (d, J = 8.0 Hz, 1H), 8.19 (d, J = 2.4 Hz, 1H), 7.93 (d, J = 8.0 Hz, 1H), 7.64 (dd, J = 8.0 Hz, J = 2.4 Hz, 2H), 7.32 (d, J = 8.0 Hz, 1H), 7.28 (d, J = 8.0 Hz, 1H), 4.20 (t, J = 7.2 Hz, 2H), 3.83 (t, J = 6.0 Hz, 2H), 1.82 (m, 2H), 1.69 (m, 2H).

[0326] General Procedure for the Synthesis of Compound PLC-41.2—2-(4-Hydroxybutyl)-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione: A 250 mL flask was equipped with a stir bar. Compound PLC-41.1 (900.0 mg, 2.1 mmol), 4-(trifluoromethyl)phenylboronic acid (780.0 mg, 4.1 mmol), Pd(dppf)Cl (107.5 mg, 0.15 mmol), and KCO (782.5 mg, 5.7 mmol) in THF / DMF / HO (60 mL / 12 mL / 6 mL) were added to the flask and degassed at room temperature. The reaction mixture was heated to 80° C. and maintained at this temperature overnight. The reaction was monitored using TLC. Upon completion, the reaction was worked up by the addition of HO (150 ml), which was added to precipitate the product. The precipitate was collected by filtration. The solid was washed with HO (200 ml) and MeOH (20 ml) and dried in a vacuum oven at 100° C. for an additional 3 hours to afford PLC-41.2 (990.0 mg, 94% yield) as a yellow solid for the next step without further purification. MS (APCI): Formula: C 29 H 20 Calculated for F3NO4 ([M+H] + )=504 Actual 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).

[0327] General Procedure for the Synthesis of Compound PLC-41.3—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 stir bar. To the flask was added compound PLC-41.2 (200.0 mg, 0.40 mmol) and DCE (20 mL). 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. Additional DCE (20 mL) and p-toluenesulfonic anhydride (519.0 mg, 1.6 mmol) were added. The reaction was cooled to room temperature. HO (100 ml) and TEA (221.0 μL, 1.6 mmol) were added. The reaction was kept at 90° C. overnight. After quenching the reaction by adding HO (150 ml), the mixture was extracted with DCM (150 ml×3). The combined organic phase was dried over anhydrous NaSO and concentrated under vacuum rotary evaporator to give PLC-41.3 as a yellow solid, which was used in the next step without further purification. MS (APCI): Chemical Formula: C 36 H 26 Calculated value for F3NO6S ([MH] - )=657 Actual 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).

[0328] General procedure for the synthesis of compound PLC-41.4—2,6-dichloro-4-(4-(1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)butoxy)benzaldehyde: A 25 mL vial was charged with PLC-41.3 (131.5 mg, 0.20 mmol) and 4-hydroxy-2,6-dichlorobenzaldehyde (42.0 mg, 0.22 mmol) in DMF (5 mL). The solution was degassed at room temperature, and KCO (41.4 mg, 0.30 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 the reaction was complete. The reaction mixture was purified by silica gel flash chromatography using 5% to 40% EtOAc in hexanes as the eluent to give pure compound PLC-41.4 as a yellow solid (27.0 mg, 20% yield over two steps). MS (APCI): Chemical Formula: C 36 H 22 Calculated value for Cl2F3NO5 ([MH] - )=676 Actual value: 676.1H NMR(400MHz,CDCl3) δ 10.37(s,1H), 8.67(d,J=8.0Hz,1H), 8.63(d,J=8.0Hz,1H), 8.26(d,J=2.4Hz,1H), 8.05(d,J=8.0Hz,1H), 7.78(bs, 4H), 7.75(m,1H), 7.49(d,J=8.0Hz,1H), 7.35(d,J=8.0Hz,1H), 6.88(s,2H), 4.26(m,2H), 4.09(m,2H), 1.96(m,4H).

[0329] General procedure for the synthesis of compound PLC-41—2-(4-(3,5-dichloro-4-(19,19-difluoro-6,7,11,12,13,19-hexahydro-5H-18|4,19|4-benzo[3′,4′]cyclohepta[1′,2′:4,5]pyrrolo[1,2-c]benzo[3′,4′]cyclohepta[1′,2′:4,5]pyrrolo[2,1-f][1,3,2]diazaborin-9-yl)phenoxy)butyl)-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione: A 50 mL two-neck round-bottom flask was equipped with an air condenser and a stir bar. To a flask were added PLC-41.4 (27.0 mg, 0.04 mmol) and Ex-7.3 (15.3 mg, 0.084 mmol), followed by anhydrous dichloromethane (5 mL). The reaction mixture was degassed at room temperature, and then p-TsOH·HO (0.2 mg, 0.002 mmol) was added. The reaction solution was maintained at this temperature for 2 hours. DDQ (5.0 mg, 0.02 mmol) was then added. The reaction was maintained at room temperature for 1 hour. BF·OEt (59 μL, 0.48 mmol) and EtN (44 μL, 0.32 mmol) were then added at room temperature. The reaction mixture was maintained at room temperature overnight. The reaction mixture was loaded onto silica gel and purified by flash chromatography using 0% to 3% EtOAc in DCM as the eluent to give pure PLC-41 as a dark purple solid (12.0 mg, 28% yield). MS(APCI):Chemical formula:C 62 H 43 Calculated value for BCl2F5N3O4 ([MH] - )=1070 Actual value: 1070.1H NMR(400MHz,CDCl2CDCl2) 8.69(d,J=8.0Hz,1H), 8.64(d,J=8.0Hz,1H), 8.28(d,J=2.4Hz,1H), 8.09(d,J=8.0Hz,1H), 8.05(m,2H), 7.79(m,5H), 7.53(d,J=8. 0Hz,1H), 7.38(m,5H), 7.30(m,2H), 7.08(s,2H), 6.48(s,2H), 4.30(bs,2H), 4.14(bs,2H), 2.64(m,4H), 2.32(bs,4H), 2.00(m,8H).

[0330] Synthesis of compound PLC-42 [ka]

[0331] General procedure for the synthesis of compound PLC-42.1—9-bromo-2-(2-(2-(2-hydroxyethoxy)ethoxy)ethyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione: A 100 mL flask was equipped with a stir bar. Compound Ex-4.3 (1.3 g, 3.4 mmol), 2-(2-(2-aminoethoxy)ethoxy)ethan-1-ol (1.0 g, 6.8 mmol), and DMAP (29.0 mg, 0.24 mmol) in DMF (25 mL) were added to the flask and degassed at room temperature. The reaction mixture was heated to 165° C. and maintained at this temperature for 2 hours. TLC and LCMS indicated completion of the reaction. The reaction was cooled to 50° C. This solution was poured into a solution of acetone (100 mL) pre-cooled using an ice-water bath. The mixture was kept at this temperature for 2 hours and then at room temperature overnight. The precipitate was collected by filtration. The solid was washed with HO (150 ml) and further dried in a vacuum oven at 100° C. for 3 hours to give PLC-42.1 (805.0 mg, 48% yield) as a brown solid for the next step without further purification. MS (APCI): Chemical Formula: C 24 H 20 Calculated value for BrNO6 ([MH] - )=498 Actual value: 498.1H NMR(400MHz,CDCl2CDCl2) 8.61(d,J=8.0Hz,1H), 8.58(d,J=8.0Hz,1H), 8.18(d,J=2.4Hz,1H), 7.91(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), 4.42(t,J=6.0Hz,2H), 3.83(t,J=6.0Hz,2H), 3.63(m,8H).

[0332] General procedure for the synthesis of compound PLC-42.2—2-(2-(2-(2-hydroxyethoxy)ethoxy)ethyl)-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione: A 250 mL flask was equipped with a stir bar. Compound 1621-36 (800.0 mg, 1.6 mmol), 4-(trifluoromethyl)phenylboronic acid (609.8 mg, 3.2 mmol), Pd(dppf)Cl (82.4 mg, 0.1 mmol), and KCO (600.0 mg, 4.4 mmol) in THF / DMF / HO (44 mL / 8.8 mL / 4.4 mL) were added to the flask and degassed at room temperature. The reaction mixture was heated to 80° C. and maintained at this temperature overnight. The reaction was monitored using TLC. Upon completion, the reaction was worked up by the addition of HO (150 ml), which was added to precipitate the product. The precipitate was collected by filtration. The solid was washed with HO (200 ml) and MeOH (20 ml) and further dried in a vacuum oven at 100° C. for 3 hours to give PLC-42.2 as a yellow solid (quantitative yield) for the next step without further purification. MS (APCI): Chemical Formula: C 31 H 24 Calculated for F3NO6 ([M+H] + )=564 Actual value: 564.1H 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), 7.96(bs,1H), 7.80(m,5H), 7.52( d,J=8.4Hz,1H), 7.37(d,J=8.4Hz,1H), 4.43(t,J=6.0Hz,2H), 3.84(t,J=6.0Hz,2H), 3.70(m,2H), 3.64(m,4H), 3.54(m,2H).

[0333] General procedure for the synthesis of compound PLC-42.3—2-(2-(2-(1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)ethoxy)ethoxy)ethyl 4-methylbenzenesulfonate: A 100 mL flask was equipped with a stir bar. To the flask was added compound 1621-41 (300.0 mg, 0.53 mmol) and NMP (8 mL). The solution was degassed at room temperature. p-Toluenesulfonic anhydride (522.2 mg, 1.6 mmol) and TEA (162.0 mg, 1.6 mmol) were added. The solution was then heated to 90° C. and maintained at this temperature overnight. The reaction was monitored using TLC and LCMS. Over extended periods, the reaction remained at 90% conversion. After adding more p-toluenesulfonic anhydride (130.0 mg), the conversion could be improved to 97%. The reaction was cooled to room temperature. H2O (100 ml) was added. The mixture was extracted with DCM (150 ml x 3). The combined organic phase was dried over anhydrous Na2SO4 and concentrated under vacuum rotary evaporator to give PLC-42.3 as a yellow solution (containing NMP as a residue), which was used in the next step without further purification. MS (APCI): Chemical Formula: C 38 H 30 Calculated values ​​for F3NO8S ([MH] - )=717 Actual value: 717.1H NMR(400MHz,CDCl2CDCl2) 8.64(d,J=8.0Hz,1H), 8.58(d,J=8.0Hz,1H), 8.26(d,J=2.4Hz,1H), 8.06(d,J=8.0Hz,1H), 7.76(m,7H), 7.51(d,J=8.4 Hz,1H), 7.34(m,3H), 4.38(t,J=6.0Hz,2H), 4.05(m,2H), 3.76(t,J=6.0Hz,2H), 3.61(m,4H), 3.54(m,2H), 2.42(s,3H).

[0334] General procedure for the synthesis of compound PLC-42.4—2,6-dichloro-4-(2-(2-(2-(1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)ethoxy)ethoxy)ethoxy)benzaldehyde: A 25 mL vial was charged with PLC-42.3 (186.6 mg, 0.26 mmol) and 4-hydroxy-2,6-dichlorobenzaldehyde (54.6 mg, 0.29 mmol) in DMF (5 mL). The solution was degassed at room temperature, and KCO (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 the reaction was complete. The reaction mixture was purified by silica gel flash chromatography using EtOAc in hexanes (0% → 40% → 60%) as the eluent to give pure compound PLC-42.4 as a yellow solid (37.0 mg, 19% yield over two steps). MS (APCI): Chemical Formula: C 38 H 26 Calculated value for Cl2F3NO7 ([MH] - )=736 Actual value: 736.1H NMR(400MHz,CDCl2CDCl2) δ 10.20(s,1H), 8.62(d,J=8.0Hz,1H), 8.57(d,J=8.0Hz,1H), 8.20(d,J=2.0Hz,1H), 8.01(d,J=8.0Hz,1H), 7.80(s,4H), 7.76(dd, J=8.0Hz,2.0Hz,1H), 7.47(d,J=8.0Hz,1H), 7.33(d,J=8.0Hz,1H), 6.69(s,2H), 4.45(t,J=6.0Hz,2H), 3.86(m,4H), 3.72(m,6H).

[0335] General procedure for the synthesis of compound PLC-42—2-(2-(2-(2-(3,5-dichloro-4-(19,19-difluoro-6,7,11,12,13,19-hexahydro-5H-18|4,19|4-benzo[3′,4′]cyclohepta[1′,2′:4,5]pyrrolo[1,2-c]benzo[3′,4′]cyclohepta[1′,2′:4,5]pyrrolo[2,1-f][1,3,2]diazaborin-9-yl)phenoxy)ethoxy)ethoxy)ethyl)-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione: A 100 mL two-neck round-bottom flask was equipped with an air condenser and a stir bar. To a flask were added PLC-42.4 (37.0 mg, 0.05 mmol) and 1605-44 (19.3 mg, 0.11 mmol), followed by anhydrous dichloromethane (5 mL). The reaction mixture was degassed at room temperature, and then p-TsOH·HO (0.3 mg, 0.003 mmol) was added. The reaction solution was maintained at this temperature for 2 hours. DDQ (6.2 mg, 0.03 mmol) was then added. The reaction was maintained at room temperature for 1 hour. BF·OEt (74 μL, 0.6 mmol) and EtN (56 μL, 0.4 mmol) were then added at room temperature. The reaction mixture was maintained at room temperature overnight. The reaction mixture was loaded onto silica gel and purified by flash chromatography using 0→6% EtOAc in DCM as the eluent to give pure PLC-42 as a dark purple solid (7.0 mg, 13% yield). MS (APCI): Formula: C 64 H 47 Calculated value for BCl2F5N3O6 ([MH] -)=1130 Actual value: 1130.1H NMR(400MHz,CDCl2CDCl2) 8.68(d,J=8.0Hz,1H), 8.63(d,J=8.0Hz,1H), 8.26(d,J=2.4Hz,1H), 8.08(d,J=8.0H z,1H), 8.04(m,2H), 7.78(bs,4H), 7.78(dd,J=8.0Hz,2.0Hz,1H), 7.50(d,J=8.0Hz,1 H), 7.37(m,5H), 7.29(m,2H), 7.07(s,2H), 6.46(s,2H), 4.46(t,J=8.4Hz,2H), 4.13 (t,J=4.4Hz,2H), 3.86(m,4H), 3.74(m,4H), 2.63(m,4H), 2.31(bs,4H), 2.04(m,4H).

[0336] Synthesis of compound PLC-43 [ka]

[0337] General procedure for the synthesis of compound PLC-43.1—2-(3-hydroxypropyl)-9-(perfluorophenyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione: A 100 mL flask was equipped with a stir bar. Compound PLC-38.1 (400.0 mg, 0.9 mmol), (perfluorophenyl)boronic acid (240.0 mg, 1.1 mmol), Pd(dba) (43.0 mg, 0.05 mmol), CsF (285.6 mg, 1.9 mmol), AgO (259.4 mg, 1.1 mmol), and (t-Bu)P (1.9 mL, 1.9 mmol) in DMF (30 mL) were added to the flask and degassed at room temperature. The reaction mixture was heated to 80°C and maintained at this temperature overnight. The reaction was monitored using TLC. Upon completion, the reaction was purified by silica gel flash chromatography using 5% to 10% to 50% to 70% EtOAc in hexanes as the eluent to afford pure compound PLC-43.1 (136.0 mg, 28% yield) as a yellow solid. MS (APCI): Chemical Formula: C 27 H 14 Calculated value for F5NO4 ([MH]- )=511 Actual 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).

[0338] General procedure for the synthesis of compound PLC-43.2—2-(3-bromopropyl)-9-(perfluorophenyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione: A 100 mL flask was equipped with a stir bar. To the flask was added compound 1644-10 (136.0 mg, 0.3 mmol), CBr4 (176.3 mg, 0.5 mmol), PPh3 (140.2 mg, 0.5 mmol), and DCE (12 mL). The solution was degassed at room temperature. The reaction was maintained at this temperature for 30 minutes. The reaction was monitored using TLC and LCMS. Upon completion, the reaction was purified by silica gel flash chromatography using 5% to 10% to 50% to 70% EtOAc in hexanes as the eluent to afford pure compound PLC-43.2 (116.0 mg, 76% yield) as a yellow solid. MS(APCI):Chemical formula:C 27 H 13 Calculated value for BrF5NO3 ([M+H] + )=573 Actual value: 573.1H NMR(400MHz,CDCl2CDCl2) 8.64(d,J=8.0Hz,1H), 8.61(d,J=8.0Hz,1H), 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).

[0339] General procedure for the synthesis of compound PLC-43—2-(3-(3,5-dichloro-4-(19,19-difluoro-6,7,11,12,13,19-hexahydro-5H-18|4,19|4-benzo[3',4']cyclohepta[1',2':4,5]pyrrolo[1,2-c]benzo[3',4']cyclohepta[1',2':4,5]pyrrolo[2,1-f][1,3,2]diazaboro[1,3,2]diazaboro ... (Phenylin-9-yl)phenoxy)propyl)-9-(perfluorophenyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione: To a 25 mL vial, PLC-1.3 (73.4 mg, 0.1 mmol), PLC-43.2 (60.0 mg, 0.1 mmol), K2CO3 (28.7 mg, 0.2 mmol), and DMF (2 mL) were added. The mixture was sonicated at room temperature for 2 minutes. It was then warmed to 75 °C and stirred at this temperature for 4 hours. TLC (50% EtOAc in hexanes) showed the reaction was complete. The reaction mixture was purified by silica gel flash chromatography using 0% to 3% EtOAc in DCM as the eluent to give pure compound PLC-43 (91.0 mg, 81% yield) as a dark purple solid. MS (APCI): Chemical Formula: C 60 H 37 Calculated value for BCl2F7N3O4 ([MH] - ) = 1077 Found value: 1077. 1H NMR (400 MHz, CDCl2CDCl2) 8.67(d,J=8.0Hz,1H), 8.63(d,J=8.0Hz,1H), 8.18(bs,1H), 8.05(m,2H), 8.01(d,J=8.0Hz,1H), 7.61(m,1H), 7.54(d,J=8.0Hz,1H), 7. 38(m,5H), 7.30(m,2H), 7.02(s,2H), 6.47(s,2H), 4.44(t,J=6.0Hz,2H), 4.22(t,J=6.0Hz,2H), 2.64(m,4H), 2.32(m,6H), 2.05(m,4H).

[0340] Synthesis of compound PLC-44 [ka]

[0341] Compound PLC-44.1: 9-(3,5-bis(trifluoromethyl)phenyl)-2-(3-hydroxypropyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione: Compound PLC-38.1 (0.4241 g, 1.0 mmol, 1 equiv.) was suspended in DMF (5 mL) and HO (0.5 mL). To the suspension was added (bis-3,5-trifluoromethyl)benzeneboronic acid (0.51586 g, 2.0 mmol, 2 equiv.), KCO (0.27642 g, 2.0 mmol, 2 equiv.), and Pd(dppf)Cl·DCM (16.33 mg, 0.02 mmol, 0.02 equiv.). The resulting mixture was subjected to three cycles of vac-filling with argon and heated with stirring at 80°C for 45 minutes. The mixture became sticky, so 15 ml of DMF was added and stirring was continued at 80°C for another 15 minutes. The reaction mixture was cooled to room temperature and concentrated by rotary evaporation. Water was added to the residual mixture and kept at room temperature for 1 hour. The precipitate was filtered to give 570 mg of a greenish-yellow solid, which was washed with MeOH to give 270 mg of pure product (48% yield). MS (APCI): Chemical Formula: C 29 H 17 Calculated for F6NO4 (M-) = 557; Found: 557. 1H NMR (400 MHz) δ 8.60(d,J=7.9Hz,1H), 8.55(d,J=8.4Hz,1H), 8.17(d,J=2.2Hz,1H), 8.03(d,J=8.1Hz,1H), 8.00(s,2H), 7.87(s,1H), 7.70(dd,J=8.7,2.1Hz, 1H), 7.47(d,J=8.6Hz,1H), 7.31(d,J=8.3Hz,1H), 4.25(t,J=6.2Hz,2H), 3.49(d,J=6.1Hz,3H), 3.08(t,J=6.8Hz,1H), 1.90(t,J=6.0Hz,2H).

[0342] Compound PLC-44.2: 9-(3,5-bis(trifluoromethyl)phenyl)-2-(3-bromopropyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione: A mixture of PLC-44.1 (558 mg, 1.0 mmol) in 48% aqueous HBr (30.0 ml) was heated to reflux at 130° C. in a heat block for 16 hours. LCMS showed >90% conversion. After cooling to room temperature, the solid was filtered, washed with water, and dried in a vacuum oven to give the desired compound containing some unreacted SM. 600 mg of a greenish-yellow solid (86% yield) was obtained. The product was used in the next step without further purification. MS (APCI): Chemical Formula: C 29 H 16 BrF6NO 34 Calculated value for (M-) = 620; Actual value: 620. 1H NMR (400MHz) δ 8.58(d,J=7.8Hz,1H), 8.53(d,J=8.4Hz,1H), 8.16(d,J=2.3Hz,1H), 8.04~7.97(m,2H), 7.86(s,1H), 7.70(dd,J=8.6,2. 2Hz,1H), 7.46(d,J=8.6Hz,1H), 7.30(d,J=8.3Hz,1H), 4.23(t,J=7.1Hz,2H), 3.45(t,J=6.8Hz,2H), 2.34~2.16(m,2H).

[0343] Compound PLC-44: 9-(3,5-bis(trifluoromethyl)phenyl)-2-(3-(3,5-dichloro-4-(19,19-difluoro-6,7,11,12,13,19-hexahydro-5H-18|4,19|4-benzo[3',4']cyclohepta[1',2':4,5]pyrrolo[1,2-c]benzo[3',4']cyclohepta[1',2':4,5]pyrrolo[2,1-f][1,3,2]diazaborinine- (9-yl)phenoxy)propyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione: Compound PLC-44.2 (46.52 mg, 0.075 mmol, 1.15 equiv.) was suspended in anhydrous DMF (2.0 mL) and PLC-1.3 (38.04 mg, 0.065 mmol, 1 equiv.), KCO (20.73 mg, 0.15 mmol, 2.3 equiv.), and NaI (4.15 mg, catalytic amount) were added. The mixture was stirred at 85 °C for 3 h under an argon atmosphere. The mixture was filtered, the solid was washed with 50 mL of water, then loaded onto a 40 g column and eluted with Hex:DCM (9:1 to DCM only). The product from the column was washed with EtOH to give 53 mg of a dark purple solid (62% yield). MS(APCI):Chemical formula:C 62 H 40 Calculated for BCl2F8N3O4 (M-) = 1124; found: 1124. 1H NMR (400 MHz) δ 8.61 (d, J = 7.8 Hz, 1H), 8.55 (d, J = 8.3 Hz, 1H), 8.16 (d, J = 2.2 Hz, 1H), 8.04 (d, J = 8.1 Hz, 1H), 8.00 (s, 2H), 7.95 (t, J = 4.7 Hz, 2H), 7.86 (s, 1H), 7.70 (dd, J = 8.6, 2.2 Hz, 1H), 7.47 (d, J = 8.6 Hz, 1H), 7.32 (d,J=8.3Hz,1H), 7.27(dt,J=7.4,3.7Hz,3H), 7.23~7.15(m,2H), 6.92(s,2H), 6.38(s,2H), 4.36( t,J=7.0Hz,2H), 4.13(t,J=6.0Hz,2H), 2.54(t,J=6.8Hz,4H), 2.24(s,4H), 1.96(t,J=7.2Hz,4H).

[0344] Synthesis of compound PLC-45: [ka]

[0345] Compound PLC-45.1: 4'-(tert-butyl)-3-nitro-[1,1'-biphenyl]-4-ol: 4-Bromo-2-nitro-phenol (5.45 g, 25.0 mmol) and 4-(tert-butyl)benzeneboronic acid (5.563 g, 31.25 mmol) were dissolved in dioxane (100 mL) at room temperature and stirred for 5 min. After a clear solution formed, Pd(PPh3)2Cl2 (0.175 g, 0.25 mmol) and 4N aqueous K2CO3 (25.0 mL, 50 mmol, 2 equiv.) were quickly added, and the mixture was degassed three times with nitrogen cycles in a Vac-Fil filter before heating at 80 °C for 4 h. After cooling to room temperature, the reaction mixture was adjusted to pH 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 (150 ml x 2). The organic layers were combined, washed with brine (25 mL), dried over anhydrous MgSO4, and concentrated under reduced pressure. The residue was dissolved in Hex:EA (95:5) (150 ml), the dark solid was filtered off by filtration through a short pad of Celite, and the filtrate was concentrated to give a yellow solid, which was triturated with hexane to give 3.8 g of a yellow solid (56% yield). MS (APCI): Formula: C 16 H 17 Calculated for NO (M-) = 271; found: 271. 1H NMR (400 MHz, chloroform-d) δ 10.57 (s, 1H), 8.32 (d, J = 2.3 Hz, 1H), 7.83 (dd, J = 8.7, 2.4 Hz, 1H), 7.50 (d, J = 1.5 Hz, 4H), 7.23 (d, J = 8.7 Hz, 1H), 1.37 (s, 9H).

[0346] Compound PLC-45.2: 4-Bromonaphthalic anhydride (10 g, 36 mmol, 1.15 equiv.), 4'-(tert-butyl)-3-nitro-[1,1'-biphenyl]-4-ol (PLC-45.1) (8.5 g, 31.32 mmol, 1 equiv.), and NaOH (0.864 g, 21.6 mmol, 0.6 equiv.) were mixed in anhydrous NMP (65 mL). Copper powder (1.371 g, 21.6 mmol, 0.6 equiv.) was added, and the resulting mixture was degassed three times with a Vac-Fil nitrogen cycle before being heated and stirred under a N atmosphere at 145 °C for 5 h and then at room temperature overnight. The reaction mixture was worked up with aqueous HCl and allowed to stand at room temperature for 12 hours. After that, a brown solid was precipitated, filtered, and washed with hot MeOH (250 ml x 3) to give a light brown solid (10.8 g, 23.1 mmol) (73% yield, 86% purity). MS (APCI): Chemical formula: C 28 H 21 Calculated for NO6 (M-) = 467; Found: 467.

[0347] Compound PLC-45.3: 6-((3-amino-4'-(tert-butyl)-[1,1'-biphenyl]-4-yl)oxy)-1H,3H-benzo[de]isochromene-1,3-dione: To a mixture of PLC-45.2 (4.885 g, 10.45 mmol, 1.0 equiv.) in 2-MeTHF (70.0 mL) and HCl (4 M, 26.1 mL, 10 equiv.), SnCl 2HO (9.4 g, 41.75 mmol, 4.0 equiv.) was added in one portion. The mixture was stirred at 90 °C for 30 min. TLC (hexane / ethyl acetate = 7:3) and LCMS indicated the reaction was complete. The white solid was filtered off and washed with EA / 2-MeTHF (1:1) (100 mL × 2). The combined organic filtrate was 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 30 minutes, filtered, and then dried under reduced pressure to give PLC-45.3 (4.5 g, 10.28 mmol) as a tan solid (98% yield). MS (APCI): Formula: C 28 H 23 Calculated for NO4 (M-) = 437; Found: 437.

[0348] Compound PLC-45.4: 9-(4-(tert-butyl)phenyl)-1H,3H-isochromeno[6,5,4-mna]xanthene-1,3-dione: To compound PLC-45.3 (1.844 g, 4.215 mmol, 1.0 equiv) in AcOH (28.5 mL) and HO (9.0 mL) was added NaNO (2.9 g, 42.15 mmol, 10 equiv) in concentrated HCl (2.445 mL) and HO (9 mL) dropwise at 0 °C and stirred for 1 hour at 0 °C. The above solution was added via dropping funnel to CuSO 5HO (4.35 g, 17.42 mmol, 4.1 equiv) in HO (175 mL), AcOH (11 mL) at 130 °C over 30 minutes. After the addition was complete, the mixture was kept stirring for another 15 minutes at the same temperature of 130° C. The mixture was filtered and washed with HO (3×100 mL) to give 0.445 g of crude product, which was triturated with EtOH to give 0.42 g of pure compound (30% yield). MS (APCI): Formula: C 28 H 20 Calculated for O4 (M-) = 420; Found: 420.

[0349] Compound PLC-45.5: 9-(4-(tert-butyl)phenyl)-2-(3-hydroxypropyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione: To compound PLC-45.4 (0.420 g, 1.0 mmol, 1.0 equiv.) in anhydrous DMSO (4 mL) was added 3-amino-1-propanol (0.300 g, 4.0 mmol, 4.0 equiv.) at room temperature, and the resulting mixture was stirred at 130 °C for 45 minutes. After the reaction was complete, the DMSO was removed by filtration. The solid was washed with water (50 ml × 3) and dried in a vacuum oven to give 0.45 g of a yellow solid (94% yield). MS (APCI): Chemical Formula: C 31 H 27Calculated for NO (M-) = 477; found: 477. 1H NMR (400 MHz, chloroform-d) δ 10.44 (s, 2H), 8.65 (d, J = 7.8 Hz, 1H), 8.60 (d, J = 8.3 Hz, 1H), 8.25 (d, J = 2.0 Hz, 1H), 8.03 (d, J = 8.0 Hz, 1H), 7.76 (dd, J = 8.6, 2.1 Hz, 1H), 7.61 (d, J = 8.3 Hz, 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), 4.4 2(t,J=6.9Hz,2H), 4.17(t,J=6.2Hz,2H), 2.54(s,6H), 2.28(s,2H), 1.40(s,9H).

[0350] Compound PLC-45.6: 2-(3-bromopropyl)-9-(4-(tert-butyl)phenyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione: A mixture of 1643-002 (0.453 g, 0.95 mmol) and 48% aqueous HBr (20 ml) was stirred and heated at 130° C. in a heat block for 8 hours. LCMS showed that SM was completely consumed. The mixture was cooled to room temperature and allowed to stand at room temperature for 16 hours. The yellow solid was filtered, washed several times with water, and dried in a vacuum oven to give 0.275 g (96% yield). The product was used in the next step without further purification. MS (APCI): Formula: C 31 H 26 Calculated for BrNO (M-) = 540; found: 540. 1H NMR (400 MHz) δ 8.59 (d, J = 7.8 Hz, 1H), 8.53 (d, J = 8.4 Hz, 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).

[0351] Compound PLC-45: 9-(4-(tert-butyl)phenyl)-2-(3-(3,5-dichloro-4-(19,19-difluoro-6,7,11,12,13,19-hexahydro-5H-18|4,19|4-benzo[3',4']cyclohepta[1',2':4,5]pyrrolo[1,2-c]benzo[3',4']cyclohepta[1',2':4,5]pyrrolo[2,1-f][1,3,2]diazaborin-9-i (( ... DMF and water were removed by rotary evaporation at 53°C, the residue was washed with 50 ml of hot water, then loaded onto a 40 g column and eluted with Hex:DCM (9:1) to DCM only (4 CV), then DCM / EtAco (99:1). The product from the column chromatography purification was washed with hot water to give 27 mg of a dark purple solid (38.5% yield). MS (APCI): Chemical formula: C 64 H 50Calculated for BClFN0 (M-) = 1044; found: 1044. H NMR (400 MHz, chloroform-d) δ 8.70 (d, J = 7.9 Hz, 1H), 8.64 (d, J = 8.4 Hz, 1H), 8.25 (d, J = 2.2 Hz, 1H), 8.09 (d, J = 7.3 Hz, 2H), 8.05 (d, J = 8.0 Hz, 1H), 7.76 (dd, J = 8.6, 2.1 Hz, 1H), 7.60 (d, J = 8.4 Hz, 2H), 7.53 (d, J = 8.6 Hz, 2H), 7.45 (d, J = 8.6 Hz, 1H). 7.35(d,J=8.4Hz,1H), 7.33~7.29(m,3H), 7.22(d,J=7.1Hz,2H), 6.95(s,2H), 6.42(s,2H), 4.47(t,J=6.8 Hz,2H), 4.21(t,J=6.0Hz,2H), 2.62(t,J=6.8Hz,4H), 2.40~2.24(m,4H), 2.09~1.97(m,4H), 1.39(s,9H).

[0352] Synthesis of compound PLC-46: [ka]

[0353] Compound PLC-46.2: 9-(3,5-bis(trifluoromethyl)phenyl)-2-(2-hydroxyethyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione: Step 1: A mixture of Ex-4.3 (0.735 g, 2.0 mmol, 1.0 equiv.) and 3-amino-1-ethanol (0.732 g, 12.0 mmol, 6.0 equiv.) was placed in a 20 mL vial with a septum cap and sealed. The resulting mixture was stirred at 160° C. for 45 minutes. After cooling to room temperature, the reaction was stirred with MeOH (10 mL) at room temperature for 15 minutes and then filtered. The crude product, PLC-46.1, was used in the next step without further purification. MS (APCI): Chemical Formula: C 20 H 12Calculated for BrNO (M-) = 410; found: 410. H NMR (400 MHz, chloroform-d) δ 8.62 (d, J = 8.3 Hz, 1H), 8.20 (d, J = 2.3 Hz, 1H), 7.93 (d, J = 7.9 Hz, 1H), 7.62 (dd, J = 8.8, 2.3 Hz, 1H), 7.32 (d, J = 8.3 Hz, 1H), 7.28 (s, 1H), 4.55–4.40 (m, 2H), 3.99 (s, 2H), 2.49 (s, 1H), 2.22 (t, J = 7.6 Hz, 1H). Step 2: At room temperature, the crude product from the previous step was mixed with DMF (5 mL), HO (0.5 mL), (bis-3,5-trifluoromethyl)benzeneboronic acid (1.031 g, 4.0 mmol, 2 equiv.), KCO (0.553 g, 4.0 mmol, 2 equiv.), and Pd(dppf)Cl·DCM (32.66 mg, 0.04 mmol, 0.02 equiv.), followed by three vac-fill argon cycles and heating and stirring at 80 °C for 45 min. The mixture became viscous, so 5 mL of DMF was added and stirring was continued at 80 °C for an additional 15 min. The reaction mixture was cooled to room temperature and concentrated on a rotary evaporator. Water was added to the residue mixture and the mixture was kept at room temperature for 1 h. The precipitate was filtered to give 1.1 g of a greenish-yellow solid, which was washed with MeOH to give 0.85 g of the desired product, PLC-46.2 (80% yield). MS(APCI):Chemical formula:C 28 H 15 Calculated for F6NO4 (M-) = 543; found: 543. 1H NMR (400 MHz, chloroform-d) δ 8.71 (d, J = 7.7 Hz, 1H), 8.65 (d, J = 8.2 Hz, 1H), 8.26 (s, 1H), 8.11 (s, 1H), 8.09 (s, 1H), 8.03 (s, 3H), 7.99 (s, 1H), 7.94 (s, 1H), 7.77 (d, J = 8.7 Hz, 1H), 7.53 (d, J = 8.8 Hz, 2H), 7.37 (d, J = 8.4 Hz, 1H), 4.49 (d, J = 5.5 Hz, 2H), 4.01 (d, J = 5.4 Hz, 2H), 3.73 (s, 1H).

[0354] Compound PLC-46: 9-(3,5-bis(trifluoromethyl)phenyl)-2-(2-(3,5-dichloro-4-(19,19-difluoro-6,7,11,12,13,19-hexahydro-5H-18|4,19|4-benzo[3',4']cyclohepta[1',2':4,5]pyrrolo[1,2-c]benzo[3',4']cyclohepta[1',2':4,5]pyrrolo[2,1-f] [1,3,2]diazaborinin-9-yl)phenoxy)ethyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione: Triphenylphosphine (39.34 mg, 0.15 mmol), PLC-1.3 (76.08 g, 0.13 mmol), and PLC-46.2 (81.51 g, 0.15 mmol) were dissolved in anhydrous toluene (2 mL), and a solution of 0.15 mL of 1 M diacetylacetone in toluene and 1 mL of anhydrous toluene was added dropwise at room temperature over 15 minutes. The resulting mixture was stirred for 16 hours under an argon atmosphere. Additional triphenylphosphine (19.73 mg, 0.075 mmol) and 0.075 mL of 1 M diacetylacetone in toluene and 0.5 mL of anhydrous toluene were added successively, and the mixture was stirred for an additional 8 hours. Purification: The RX mixture was loaded onto an 80 g SiO column and eluted with Hex:DCM (7:3), (1:4), then DCM alone. Fractions containing the desired compound were collected and concentrated. The dark purple solid was washed with water, then MeOH, and dried in a vacuum oven to give 43 mg of a dark brownish-purple solid (42% yield). MS (APCI): Chemical Formula: C 61 H 38Calculated for BCl2F8N3O4 (M-) = 1110, found: 1110. 1H NMR (400 MHz, chloroform-d) δ 8.74 (d, J = 7.9 Hz, 1H), 8.68 (d, J = 8.3 Hz, 1H), 8.26 (d, J = 2.2 Hz, 1H), 8.11 (d, J = 8.0 Hz, 1H), 8.09-8.03 (m, 4H), 7.95 (s, 1H), 7.77 (dd, J = 8.6 Hz, 2.2 Hz, 1H), 7.53 (d, J = 8.6 Hz, 1H), 7.38 (d, J = 8. 3Hz,1H), 7.35~7.26(m,4H), 7.21(dd,J=6.8,2.0Hz,2H), 7.11(s,2H), 6.39(s,2H), 4.72(t,J =6.2Hz,2H), 4.43(t,J=6.2Hz,2H), 2.61(t,J=6.8Hz,4H), 2.29(s,4H), 2.02(q,J=6.8Hz,4H).

[0355] Synthesis of compound PLC-47: [ka]

[0356] Compound PLC-47.1: (9-Bromo-2-(6-hydroxyhexyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione): Compound Ex-4.3 (6.534 mmol, 2.401 g), 6-aminohexan-1-ol (13.08 mmol, 1533 mg), and DMAP (1.962 mmol, 240 mg) were mixed with DMF. The crude product was filtered off and washed with water, and the wet precipitate was used in the next step without further purification. MS (APCI): Chemical Formula: C 24 H 20 Calculated for BrNO4 (M+H) = 466; Found: 466.

[0357] Compound PLC-47.2: (2-(6-hydroxyhexyl)-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione): Compound PLC-47.1 (assuming 100% yield, 6.534 mmol, 3.047 g), (4-(trifluoromethyl)phenyl)boronic acid (13.068 mmol, 2.482 g), KCO (17.969 mmol, 2483 mg), and Pd(dppf)Cl (0.4574 mmol, 335 mg) in THF (120 mL) / DMF (24 mL) / HO (12 mL) were combined at 80 °C in a manner similar to that described above. After adding water and filtering, the resulting precipitate was washed with water and then with methanol. The product was dried by suction and then vacuum dried. Obtained 1.191 g (34% yield based on compound 29.3, 2 steps). MS (APCI): Chemical formula: C 31 H 24 Calculated for F3NO4 (M+H) = 532; Found: 532.

[0358] Compound PLC-47.3: (2-(6-Bromohexyl)-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione): A 250 mL two-neck round-bottom flask was equipped with a stir bar and fitted with a gas adapter / finned condenser and a flow controller. Compound PLC-47.2 (2.239 mmol, 1.190 g) was added to the flask, followed by 48% HBr / HO (30 mL). The heat block was set to 130 °C, and the reaction mixture was stirred at this temperature for 3 hours. Another portion of 48% HBr / HO (30 mL) was added, and the reaction mixture was stirred at 130 °C overnight. The reaction mixture was cooled to room temperature and diluted with water (approximately 100 mL). The precipitate was then filtered off and washed with water and then methanol. The product was loaded onto approximately 25 g of silica gel in a loader. Purification was carried out by flash chromatography on silica gel (120 g, solids, equilibrated 0% EtOAc / DCM, 0% (2 CV) to 10% EtOAc / DCM (20 CV)). The fractions containing the product were collected and evaporated to dryness in vacuo. A material of approximately 80% purity was obtained. 1.073 g (80% yield) of a yellow solid was obtained. MS (APCI): Formula: C 31 H 23 Calculated for BrF3NO3 (M+H) = 594; Found: 594. 1H NMR (400 MHz, 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), 7.84~7.73(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).

[0359] Compound PLC-47.4: (2,6-Dichloro-4-((6-(1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)hexyl)oxy)benzaldehyde): Compound PLC-47.4 was synthesized in a manner similar to that for Compound 34.4 from compound PLC-47.3 (0.200 mmol, 119 mg), 2,6-dichloro-4-hydroxybenzaldehyde (0.300 mmol, 57 mg), and KCO (0.260 mmol, 36 mg) in dry DMF (10 mL). The crude compound was dissolved in DCM and loaded onto approximately 5 g of silica gel in a loader. Purification was performed by flash chromatography on silica gel (80 g, solids, equilibrated 70% DCM / hexane, eluting 70% (2 CV) to 100% DCM / hexane (5 CV) → isocratic 100% DCM / hexane (5 CV) to 0% EtOAc / DCM (0 CV) to isocratic 0% EtOAc / DCM (5 CV) → 10% EtOAc / DCM (20 CV)). Fractions containing the product were evaporated to dryness in vacuo. 113 mg (60% yield) of a yellow solid was obtained. MS (APCI): Formula: C 38 H 26 Calculated for Cl2F3NO5 (M+H) = 704; Found: 704. 1H NMR (400 MHz, TCE) δ 10.37(s,1H), 8.64(d,J=7.9Hz,1H), 8.59(d,J=8.4Hz,1H), 8.25(d,J=2.2Hz,1H), 8.05(d,J=8.0Hz,1H), 7.78(dd,J=11.2,1.9Hz,5H), 7 .50(d,J=8.6Hz,1H), 7.36(d,J=8.3Hz,1H), 6.92(s,2H), 4.23~4.11(m,2H), 4.02(t,J=6.4Hz,2H), 1.89~1.70(m,4H), 1.59~1.45(m,4H).

[0360] Compound PLC-47: (2-(6-(3,5-dichloro-4-(19,19-difluoro-6,7,11,12,13,19-hexahydro-5H-18|4,19|4-benzo[3',4']cyclohepta[1',2':4,5]pyrrolo[1,2-c]benzo[3',4']cyclohepta[1',2':4,5]pyrrolo[2,1-f][1,3,2]diazabo Compound PLC-47.4 (0.1164 mmol, 82 mg), 1,4,4-trifluoromethyl-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione (4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione) in a similar manner to that described above was prepared by reacting compound PLC-47.4 (0.1164 mmol, 82 mg), 1,4,4-trifluoromethyl-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione in dry DCM (20 mL) at room temperature followed by 50° C. The crude reaction mixture was diluted with approximately 25% hexane and loaded onto approximately 15 g of silica gel in a loader. Flash chromatography on silica gel (80 g, solids content, equilibrated 70% DCM / hexane, eluted 70% (2 CV) to 100% DCM / hexane (5 CV), isocratic 100% DCM / hexane (5 CV)). Purification was carried out with 100% DCM / hexane (isocratic) in 0.5% EtOAc. Fractions containing the product were evaporated to dryness in vacuo. 79 mg (62% yield) of a deep red solid was obtained. MS (APCI): Chemical formula: C 64 H 47Calculated for BCl2F5N3O4 (M+H) = 1098; found: 1098. 1H NMR (400 MHz, TCE) δ 8.66 (d, J = 7.9 Hz, 1H), 8.61 (d, J = 8.3 Hz, 1H), 8.26 (d, J = 2.1 Hz, 1H), 8.10-8.01 (m, 3H), 7.78 (dd, J = 9.4, 1.7 Hz, 5H), 7.55-7.46 (m, 5H), 7.43-7.32 (m, 5H), 7.33-7.25 (m, 2H), 7.07 (s, 2H). H), 6.48(s,2H), 4.20(t,J=7.7Hz,2H), 4.06(t,J=6.3Hz,2H), 2.63(t,J=6.9Hz,4H), 2.42~2 .19(m,4H), 2.08~2.00(m,2H), 1.88(q,J=7.3Hz,2H), 1.85~1.73(m,2H), 1.67~1.49(m,4H).

[0361] Synthesis of compound PLC-48 [ka]

[0362] Compound PLC-48.2 (tert-butyl 4-(2-(3-(3,5-dichloro-4-formylphenoxy)propyl)-1,3-dioxo-2,3-dihydro-1H-xantheno[2,1,9-def]isoquinolin-9-yl)benzoate): Compound PLC-48.2 was synthesized in a manner similar to the procedure described above from compound PLC-48.1 (0.1471 mmol), 2,6-dichloro-4-hydroxybenzaldehyde (0.441 mmol, 84 mg), and K2CO3 (0.4120 mmol, 57 mg) in dry DMF (10 mL). The crude reaction was diluted with crushed ice (approximately 50 g). Once all the ice had melted, the crude product was isolated by centrifugation. The product was dissolved in DCM and evaporated to dryness in vacuo. A quantitative yield of a yellow solid was obtained. MS (APCI): Chemical Formula: C 39 H 29Cl2NO7についての calculated value (M+H)=694; measured value: 694. 1H NMR (400MHz, TCE) δ 10.37(s,1H), 8.64(d,J=7.9Hz,1H), 8.59(d,J=8.3Hz,1H), 8.28(d,J=2.2Hz,1 H), 8.13(d,J=8.1Hz,2H), 8.07(d,J=8.0Hz,1H), 7.81(dd,J=8.6,2.1Hz,1H), 7. 75(d,J=8.2Hz,2H), 7.52(d,J=8.6Hz,1H), 7.38(d,J=8.3Hz,1H), 6.85(s,2H), 4 .39(t,J=6.7Hz,2H), 4.18(t,J=5.9Hz,2H), 2.28(p,J=5.9Hz,2H), 1.64(s,9H).

[0363] Compound PLC-48 (tert-butyl 4-(2-(3-(3,5-dichloro-4-(19,19-difluoro-6,7,11,12,13,19-hexahydro-5H-18|4,19|4-benzo[3',4']cyclohepta[1',2':4,5]pyrrolo[1,2-c]benzo[3',4']cyclohepta[1',2':4,5]pyrrolo[2,1-f][1,3,2]diazaborinine) Compound PLC-48 was prepared in a similar manner to the procedure described above by reacting compound PLC-48.2 (0.1471 mmol, 102 mg), 1,4,5,6-tetrahydro-1H-xantheno[2,1,9-def]isoquinolin-9-yl)benzoate (1,3-dioxo-2,3-dihydro-1H-xantheno[2,1,9-def]isoquinolin-9-yl)benzoate with compound PLC-48.2 (0.1471 mmol, 102 mg), 1,4,5,6-tetrahydro-1H-xantheno[2,1,9-def]isoquinolin-9-yl)benzoate (1,3-dioxo-2,3-di ... This compound was synthesized from dihydrobenzo[6,7]cyclohepta[1,2-b]pyrrole (Ex-7.3, 0.3090 mmol, 57 mg) and TFA (1% v / v), followed by DDQ (0.2501 mmol, 57 mg), 2×EtN (1.177 mmol, 0.164 mL), and BF OEt (1.765 mmol, 0.218 mL). The crude reaction mixture was diluted with hexane and loaded onto approximately 20 g of silica gel in a loader. Purification was achieved by flash chromatography on silica gel (220 g, solids, equilibrated with 10% EtOAc / hexane, eluted with 10% (2 CV) to 30% EtOAc / hexane (40 CV)). Fractions containing pure product were evaporated to dryness in vacuo. 80 mg (50% yield) was obtained. MS (APCI): Chemical Formula: C 65 H 50Calculated for BCl2F2N3O6 (M+H) = 1088; found: 1088. 1H NMR (400 MHz, TCE) δ 8.69 (d, J = 7.8 Hz, 1H), 8.63 (d, J = 8.3 Hz, 1H), 8.28 (d, J = 2.2 Hz, 1H), 8.16-8.10 (m, 2H), 8.09 (d, J = 8.1 Hz, 1H), 8.05 (t, J = 4.7 Hz, 2H), 7.80 (dd, J = 8.6, 2.1 Hz, 1H), 7.77-7.71 (m, 2H), 7.51 (d, J = 8. 6Hz,1H), 7.42~7.33(m,5H), 7.33~7.25(m,2H), 7.01(s,2H), 6.47(s,2H), 4.44(t,J=6.9Hz,2H), 4.22(t,J=6.0Hz,2H), 2.63(t,J=6.9Hz,4H), 2.40~2.24(m,6H), 2.11~2.00(m,4H), 1.62(s,9H).

[0364] Synthesis of compound PLC-49: [ka]

[0365] Compound PLC-49.1 (9-(4-butylphenyl)-2-(3-hydroxypropyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione): Compound PLC-49.1 was synthesized in a manner similar to the procedure described above from compound PLC-38.1 (1.500 mmol, 636 mg), (4-butylphenyl)boronic acid (3.00 mmol, 534 mg), K2CO3 (4.125 mmol, 570 mg), and Pd(dppf)Cl2 (0.105 mmol, 77 mg) in THF (30 mL) / DMF (6 mL) / water (3 mL) 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): Chemical Formula: C 31 H 27Calculated for NO (M+H) = 478; found: 478. 1H NMR (400 MHz, TCE) δ 8.66 (d, J = 7.9 Hz, 1H), 8.61 (d, J = 8.4 Hz, 1H), 8.26 (d, J = 2.1 Hz, 1H), 8.06 (d, J = 8.0 Hz, 1H), 7.79 (dd, J = 8.6, 2.1 Hz, 1H), 7.61 (d, J = 7.9 Hz, 2H), 7.48 (d, J = 8.6 Hz, 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), 2.06~1.92(m,2H), 1.75~1.64(m,2H), 1.42(h,J=7.4Hz,2H), 0.98(t,J=7.3Hz,3H).

[0366] Compound PLC-49.2 (3-(9-(4-butylphenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)propyl 4-methylbenzenesulfonate): A 100 mL two-neck 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 PLC-49.1 (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 EtN (1.463 mmol, 0.20 mL) was added. The reaction mixture was stirred under argon, the heat block was set to 90 °C, and stirred at this temperature for 1 h. The reaction was cooled to room temperature and loaded onto approximately 15 g of silica gel in a loader. Purification was carried out by flash chromatography on silica gel (80 g, solids, equilibrated with 0% EtOAc / DCM, eluted with 0% (2 CV) to 10% EtOAc / DCM (10 CV)). The product-containing fractions were evaporated to dryness in vacuo. 157 mg of a yellow solid (77% yield) was obtained. MS (APCI): Chemical formula: C 38 H 33Calculated for NO6S (M+H) = 632; found: 632. 1H NMR (400 MHz, TCE) δ 8.61 (d, J = 7.9 Hz, 1H), 8.56 (d, J = 8.4 Hz, 1H), 8.24 (d, J = 2.2 Hz, 1H), 8.04 (d, J = 8.1 Hz, 1H), 7.81-7.72 (m, 3H), 7.61 (d, J = 8.1 Hz, 2H), 7.47 (d, J = 8.6 Hz, 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. 19~2.07(m,2H), 1.76~1.64(m,2H), 1.42(h,J=7.3Hz,2H), 0.98(t,J=7.4Hz,3H).

[0367] Compound PLC-49.3 (4-(3-(9-(4-butylphenyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)propoxy)-2,6-dichlorobenzaldehyde): Compound PLC-49.3 was synthesized in a manner similar to the procedure described above from PLC-49.2 (0.122 mg, 77 mg), 2,6-dichloro-4-hydroxybenzaldehyde (0.366 mmol, 70 mg), and KCO (0.341 mmol, 47 mg) in dry DMF (10 mL). The crude product was loaded onto approximately 15 g of silica gel in a loader. Purification was achieved by flash chromatography on silica gel (80 g, solids, equilibrated with 0% EtOAc / DCM, eluted with 0% (2 CV) to 10% EtOAc / DCM (10 CV)). The fractions containing the product were evaporated to dryness in vacuo to give 60 mg (76% yield) of a yellow solid. MS (APCI): Chemical formula: C 38 H 29The calculated value of Cl2NO5 (M+H) is 650; the measured value is 650. ¹H NMR (400MHz, TCE) δ 10.37 (s, ¹H), 8.63 (d, J=7.9Hz, ¹H), 8.58 (d, J=8.3Hz, ¹H), 8.26 (d, J=2.1Hz, ¹H), 8.06 (d, J=8.1Hz, ¹H), 7.79 (dd, J=8.6, 2.1Hz, ¹H), 7.64~7.58 (m, 2H), 7.48 (d, J=8.6Hz, 1H), 7.36 (d, J=7.2Hz, 1H). H), 7.34(d,J=7.1Hz,2H), 6.85(s,2H), 4.39(t,J=6.8Hz,2H), 4.18(t,J=6.0Hz,2H), 2.70(t,J=7 .8Hz,2H), 2.28(p,J=6.5Hz,2H), 1.73~1.62(m,2H), 1.42(h,J=7.4Hz,2H), 0.98(t,J=7.3Hz,3H).

[0368] Compound PLC-49 (9-(4-butylphenyl)-2-(3-(3,5-dichloro-4-(19,19-difluoro-6,7,11,12,13,19-hexahydro-5H-18|4,19|4-benzo[3',4']cyclohepta[1',2':4,5]pyrrolo[1,2-c]benzo[3',4']cyclohepta[1',2':4,5]pyrrolo[2,1-f][1,3,2]diazaborin-9-yl)phenoxy)propyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione): Compound PLC-49 was prepared by the following procedure: The compound was synthesized in a similar manner to compound 32 from compound PLC-49.3 (0.0922 mmol, 60 mg), 1,4,5,6-tetrahydrobenzo[6,7]cyclohepta[1,2-b]pyrrole (Ex-7.3, 0.194 mmol, 36 mg), and TFA (0.2% v / v) at room temperature, followed by DDQ (0.157 mmol, 36 mg), 2×EtN (0.738 mmol, 0.10 mL), and BF OEt (1.107 mmol, 0.14 mL) in dry DCM (20 mL) at room temperature and then 50 °C. The crude reaction mixture was loaded onto approximately 30 g of silica gel in a loader. The product was purified by flash chromatography on silica gel (120 g, solids, equilibrated with 0% EtOAc / hexane, eluted with 0% (2 CV) to 5% EtOAc / DCM (30 CV)). The fractions containing the product were evaporated to dryness in vacuo to give 42 mg (44% yield) of a deep red solid. MS (APCI): Chemical formula: C 64 H 50Calculated for BCl2F2N3O4 (M+H) = 1044; found: 1044. 1H NMR (400 MHz, TCE) δ 8.67 (d, J = 7.8 Hz, 1H), 8.62 (d, J = 8.3 Hz, 1H), 8.25 (d, J = 2.1 Hz, 1H), 8.12-8.01 (m, 3H), 7.78 (dd, J = 8.6, 2.1 Hz, 1H), 7.65-7.56 (m, 2H), 7.48 (d, J = 8.6 Hz, 1H), 7.42-7.24 (m, 9H), 7.01 (s, 2H), 6.4 7(s,2H), 4.45(s,2H), 4.22(t,J=6.0Hz,6H), 2.70(t,J=7.8Hz,2H), 2.64(t,J=6.8Hz,4H), 2.42~ 2.23(m,6H), 2.11~1.97(m,4H), 1.73~1.62(m,2H), 1.42(h,J=7.3Hz,2H), 0.98(t,J=7.3Hz,3H).

[0369] Synthesis of compound PLC-50: [ka]

[0370] Compound PLC-50.1 (2-(3-hydroxypropyl)-9-(4-(pentyloxy)phenyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione): Compound PLC-50.1 was synthesized in a manner similar to the procedure described above from compound PLC-38.1 (1.500 mmol, 6360 mg), (4-(pentyloxy)phenyl)boronic acid (3.00 mmol, 624 mg), K2CO3 (4.125 mmol, 570 mg), and Pd(dppf)Cl2 (0.105 mmol, 77 mg) in THF (30 mL) / DMF (6 mL) / water (3 mL) at 80 °C. The precipitated compound was filtered off, washed with water, and dried in vacuo. 730 mg (96% yield) of a tan solid was obtained. MS (APCI): Chemical Formula: C 32 H 29Calculated for NO5 (M+H) = 508; found: 508. 1H NMR (400 MHz, TCE) δ 8.66 (d, J = 7.9 Hz, 1H), 8.61 (d, J = 8.4 Hz, 1H), 8.21 (d, J = 2.1 Hz, 1H), 8.06 (d, J = 8.0 Hz, 1H), 7.75 (dd, J = 8.6, 2.1 Hz, 1H), 7.65-7.57 (m, 2H), 7.47 (d, J = 8.6 Hz, 1H), 7.36 (d, J = 8.4 Hz, 1H), 7. 10~6.99(m,2H), 4.33(t,J=6.1Hz,2H), 4.03(t,J=6.6Hz,2H), 3.62~3.51(m,2H), 3.25(t,J=6 .9Hz,1H), 2.08~1.91(m,2H), 1.84(p,J=6.7Hz,2H), 1.55~1.34(m,4H), 0.97(t,J=7.1Hz,3H).

[0371] Compound PLC-50.2 (3-(1,3-dioxo-9-(4-(pentyloxy)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)propyl 4-methylbenzenesulfonate): Compound PLC-50.2 was synthesized in a manner similar to that for Compound 46.2 from Compound PLC-50.1 (1.550 mmol, 787 mg), 4-methylbenzenesulfonic anhydride (6.202 mmol, 2024 mg), and EtN (6.977 mmol, 0.97 mL) in dry DCE (20 mL) at 90 °C. The crude product was loaded onto approximately 65 g of silica gel in a loader. Purification was performed by flash chromatography on silica gel (120 g, solids, equilibrated with 0% EtOAc / DCM, eluted from 0% (2 CV) to 10% EtOAc / DCM (10 CV) isocratic to 10%). The product-containing fractions were evaporated to dryness in vacuo to give 528 mg (51% yield) of a yellow solid. MS (APCI): Chemical Formula: C 39 H 35Calculated for NO7S (M+H) = 662; found: 662. 1H NMR (400 MHz, TCE) δ 8.58 (d, J = 7.8 Hz, 1H), 8.53 (d, J = 8.4 Hz, 1H), 8.17 (d, J = 2.2 Hz, 1H), 8.00 (d, J = 8.1 Hz, 1H), 7.79-7.75 (m, 2H), 7.73 (dd, J = 8.8, 2.3 Hz, 1H), 7.63-7.57 (m, 2H), 7.43 (d, J = 8.6 Hz, 1H) ), 7.35~7.28(m,3H), 7.08~7.01(m,2H), 4.25~4.13(m,4H), 4.03(t,J=6.6Hz,2H), 2.42(s ,3H), 2.12(p,J=6.6Hz,2H), 1.90~1.77(m,2H), 1.55~1.34(m,4H), 0.97(t,J=7.1Hz,3H).

[0372] Compound PLC-50.3 (2,6-dichloro-4-(3-(1,3-dioxo-9-(4-(pentyloxy)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)propoxy)benzaldehyde): Compound PLC-50.3 was synthesized in a manner similar to the procedure described above from compound PLC-50.2 (0.180 mmol, 119 mg), 2,6-dichloro-4-hydroxybenzaldehyde (0.539 mmol, 103 mg), and KCO (0.503 mmol, 70 mg) in dry DMF (10 mL). The crude product was loaded onto approximately 15 g of silica gel in a loader. Purification was performed by flash chromatography on silica gel (80 g, solids, equilibrated with 0% EtOAc / DCM, eluted with 0% (2 CV) to 15% EtOAc / DCM (10 CV)). The fractions containing the product were evaporated to dryness in vacuo to give 103 mg (84% yield) of a yellow solid. MS (APCI): Chemical formula: C 39 H 31Calculated value of Cl2NO6 (M+H)=680; measured value: 680. 1H NMR (400MHz, TCE) δ 10.37(s,1H), 8.62(d,J=7.9Hz,1H), 8.57(d,J=8.3Hz,1H), 8.20(d,J=2.2Hz,1H), 8.04( d,J=8.1Hz,1H), 7.65~7.58(m,2H), 7.46(d,J=8.6Hz,1H), 7.35(d,J=8.4Hz,1H), 7.08~7. 02(m,2H), 6.85(s,2H), 4.38(t,J=6.8Hz,2H), 4.18(t,J=6.0Hz,2H), 4.03(t,J=6.6Hz,2H ), 2.28(p,J=6.5Hz,2H), 1.84(p,J=6.7Hz,2H), 1.55~1.35(m,4H), 0.97(t,J=7.1Hz,3H).

[0373] Compound PLC-50 (2-(3-(3,5-dichloro-4-(19,19-difluoro-6,7,11,12,13,19-hexahydro-5H-18|4,19|4-benzo[3',4']cyclohepta[1',2':4,5]pyrrolo[1,2-c]benzo[3',4']cyclohepta[1',2':4,5]pyrrolo[2,1-f][1,3,2]diazaborin-9-yl)phenoxy)propyl)-9-(4-(pentyloxy)phenyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione): This compound was synthesized in a similar manner to compound 32 from compound PLC-50.3 (0.150 mmol, 102 mg), 1,4,5,6-tetrahydrobenzo[6,7]cyclohepta[1,2-b]pyrrole (Ex-7.3, 0.315 mmol, 58 mg), and TFA (0.25% v / v) at room temperature, followed by DDQ (0.255 mmol, 58 mg), 2×EtN (1.199 mmol, 0.17 mL), and BF OEt (1.798 mmol, 0.22 mL) in dry DCM (20 mL) at room temperature and then 50 °C. The crude reaction mixture was loaded onto approximately 30 g of silica gel in a loader. Purification was performed by flash chromatography on silica gel (120 g, solids, equilibrated and run 0% EtOAc / DCM isocratic). The product-containing fractions were evaporated to dryness in vacuo. 127 mg (79% yield) of a deep red solid was obtained. MS (APCI): Chemical formula: C 65 H 52The calculated value (M+H) of BCl2F2N3O5 is 1074; the measured value is 1074. ¹H NMR (400MHz, TCE) δ 8.67 (d, J=7.9Hz, 1H), 8.61 (d, J=8.3Hz, 1H), 8.20 (d, J=2.2Hz, 1H), 8.11~8.00 (m, 3H), 7.74 (dd, J=8.6, 2.1Hz, 1H), 7.63~7.58 (m, 2H), 7.46 (d, J=8.6Hz, 1H), 7.41~7.33 (m, 5H), 7.33~7.26 (m, 2H), 7.04 (d, J=8.9Hz, 2.1Hz, 1H). H), 7.02(s,2H), 6.47(s,2H), 4.44(t,J=6.9Hz,2H), 4.22(t,J=6.0Hz,2H), 4.03(t,J=6.6Hz,2H), 2.64(t,J =6.7Hz,4H), 2.40~2.22(m,6H), 2.12~1.98(m,4H), 1.90~1.79(m,2H), 1.53~1.36(m,4H), 1.01~0.93(m,3H).

[0374] Synthesis of compound PLC-51:

change

[0375] Compound PLC-51.1 (6-(2-amino-4-(tert-butyl)phenoxy)-2-(3-hydroxypropyl)-1H-benzo[de]isoquinoline-1,3(2H)-dione): A 100 mL two-neck 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 PLC-26.2 (2.559 mmol, 925 mg), 3-aminopropan-1-ol (5.119 mmol, 0.391 mL), and DMAP (0.768 mmol, 94 mg), followed by 200 proof ethanol (20 mL). The reaction was stirred under argon and the heat block was set to 95° C. The reaction mixture was stirred at this temperature for 2 hours and then cooled to room temperature. The reaction mixture was quenched with 6H HCl (3 mL) and diluted with water (approximately 100 mL). The resulting precipitate was filtered off and washed with water. The precipitate was dried in vacuo to give a tan solid (quantitative yield). MS (APCI): Formula: C 25 H 26 Calculated for N2O4 (M+H) = 419; found: 419. 1H NMR (400 MHz, TCE) δ 8.80 (dd, J = 8.4, 1.2 Hz, 1H), 8.67 (dd, J = 7.3, 1.2 Hz, 1H), 8.46 (d, J = 8.3 Hz, 1H), 7.84 (dd, J = 8.4, 7.3 Hz, 1H), 7.02 to 6.92 (m, 3H), 6.87 (dd, J = 8.4, 2.2 Hz, 1H), 4.31 (t, J = 6.2 Hz, 2H), 3.56 (q, J = 5.0 Hz, 2H), 1.97 (p, J = 6.0 Hz, 2H), 1.35 (s, 9H).

[0376] Compound PLC-51.2 (9-(tert-butyl)-2-(3-hydroxypropyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione): A 40 mL vial was placed in a stir bar. To the vial was added NaNO (11.291 mmol, 779 mg) and water (4 mL). The vial was stirred in an ice-water bath at 0 °C. A separate 40 mL vial was also placed in a stir bar. To this vial was added compound PLC-51.1 (1.505 mmol, 630 mg), acetic acid (12 mL), and concentrated HCl (7.527 mmol, mL). The vial was stirred at room temperature for several minutes, then placed in an ice-water bath and stirred at 0 °C for 1 minute. Aqueous NaNO was added to the vial over 10 minutes with stirring at 0 °C. The diazo solution was stirred at 0 °C for 1 hour. Meanwhile, a 250 mL two-neck round-bottom flask was fitted with a finned condenser, an addition funnel, and a stir bar. CuSO₄·5H₂O (10.237 mmol, 2.556 g) and water (35 mL) were added to the flask. The solution was stirred at room temperature. Approximately 15 min before the end of the 1-h diazotization, the copper sulfate solution was heated to 130 °C (heat block temperature). The diazotization solution was transferred to the addition funnel and added to the reaction mixture over approximately 15 min with rapid stirring. The reaction mixture was stirred for an additional 1 min and then placed in a room-temperature water bath. Once the reaction had cooled to room temperature, the product was isolated by filtration. The crude product was a mixture of the desired alcohol and acetate ester. The crude product was dispersed in methanol and treated with excess K₂CO₃ at 60 °C to cleave the ester. The reaction was diluted with water, and the product was filtered off and washed with water. The crude product was redissolved in DCM and evaporated in vacuo onto silica gel. Purification was carried out by flash chromatography on silica gel (120 g, solid, equilibrated 0% EtOAc / DCM, eluted 0% (2 CV) → 75% EtOAc / DCM (20 CV)). Fractions containing the product were evaporated to dryness in vacuo. 379 mg (37% yield) of a yellow solid was obtained. MS (APCI): Formula: C 25 H 23Calculated for NO4 (M+H) = 419; Found: 419. 1H NMR (400 MHz, TCE) δ 8.65(d,J=7.8Hz,1H), 8.60(d,J=8.4Hz,1H), 8.07(d,J=2.3Hz,1H), 8.01(d,J=8.0Hz,1H), 7.63(dd,J=8.7,2.2Hz,1H), 7.37(d,J=8.7 Hz,1H), 7.34(d,J=8.3Hz,1H), 4.33(t,J=6.1Hz,2H), 3.57(q,J=6.1Hz,2H), 3.26(t,J=6.9Hz,1H), 1.98(p,J=5.9Hz,2H), 1.44(s,9H).

[0377] Compound PLC-51.3 (2-(3-bromopropyl)-9-(tert-butyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione): A 100 mL two-neck 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 PLC-51.2 (0.483 mmol, 194 mg) and carbon tetrabromide (0.725 mmol, 240 mg), followed by dry DCE (20 mL). The reaction mixture was stirred at room temperature under argon, and triphenylphosphine (0.725 mmol, 190 mg) was added. The reaction mixture was stirred at room temperature for 30 minutes. The reaction mixture was loaded onto approximately 15 g of silica gel in a loader. Purification was carried out by flash chromatography on silica gel (120 g, solids, equilibrated with 0% EtOAc / DCM, eluted with 0% (2 CV) to 10% EtOAc / DCM (20 CV)). Fractions containing the product were evaporated to dryness in vacuo. 149 mg (66% yield) of a yellow solid was obtained. MS (APCI): Formula: C 25 H 22 Calculated for BrNO3 (M+H) = 464; Found: 464.

[0378] Compound PLC-51 (9-(tert-butyl)-2-(3-(3,5-dichloro-4-(19,19-difluoro-6,7,11,12,13,19-hexahydro-5H-18|4,19|4-benzo[3',4']cyclohepta[1',2':4,5]pyrrolo[1,2-c]benzo[3',4']cyclohepta[1',2':4,5]pyrrolo[2,1-f][1,3,2]diazaborin-9-yl)phenoxy)propyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione): Compound PLC-51 was prepared in a manner similar to the procedure described above using dried DMSO. This compound was synthesized from compound PLC-51.3 (0.391 mmol, 148 mg), 3,5-dichloro-4-(19,19-difluoro-6,7,11,12,13,19-hexahydro-5H-18|4,19|4-benzo[3',4']cyclohepta[1',2':4,5]pyrrolo[1,2-c]benzo[3',4']cyclohepta[1',2':4,5]pyrrolo[2,1-f][1,3,2]diazaborin-9-yl)phenol (PLC-1.3, 0.446 mmol, 261 mg), and K2CO3 (0.382 mmol, 53 mg) in F (10 mL). The crude reaction mixture was diluted with water, and the product was filtered off. The precipitate was dissolved in DCM and evaporated to dryness in vacuo. The product was dissolved in DCM, loaded onto approximately 20 g of silica gel in a loader, and purified by flash chromatography on silica gel (120 g, solids, equilibrated 0% EtOAc / DCM, eluted 0% (2 CV) to 5% EtOAc / DCM (50 CV)). The product-containing fractions were evaporated to dryness in vacuo. 153 mg (50% yield) of a deep red solid was obtained. MS (APCI): Chemical formula: C 58 H 46Calculated for BCl2F2N3O4 (M+H) = 968; Found: 968. 1H NMR (400 MHz, TCE) δ 8.67(d,J=7.9Hz,1H), 8.60(d,J=8.3Hz,1H), 8.10~7.98(m,4H), 7.62(dd,J=8.8,2.2Hz,1H), 7.40~7.25(m,8H), 7.02(s,2H), 6.4 8(s,2H), 4.43(t,J=7.0Hz,2H), 4.21(t,J=6.0Hz,2H), 2.70~2.59(m,4H), 2.33(t,J=6.7Hz,6H), 2.12~1.98(m,4H), 1.44(s,9H).

[0379] Synthesis of compound PLC-52: [ka] [ka]

[0380] Compound PLC-52.1 (5,11-dibromo-1H,3H-isochromeno[6,5,4-mna]xanthene-1,3-dione): A 2 L, two-neck round-bottom flask was equipped with a stir bar and a long-finned condenser. 1H,3H-isochromeno[6,5,4-mna]xanthene-1,3-dione (Ex-1.3, synthesized according to RSC Adv., 2014, 4, 53072-53078) (34.688 mmol, 10.00 g) was added to the flask, followed by ortho-dichlorobenzene (1000 mL). The reaction mixture was stirred at room temperature, and Br2 (416.26 mmol, 21.3 mL) was added. The second neck was stoppered, and the reaction mixture was heated to 75 °C open to the atmosphere using an aluminum heating block over the weekend. The reaction mixture was cooled to room temperature, and the solid was filtered off. The filtrate was diluted with hexane (approximately 20% of the volume) and a second precipitate was filtered off. Both of these precipitates were dried in vacuo at 100°C. Orange solid, 10.866g total (69.9% yield). Both showed similar LCMS and NMR. MS (APCI): Formula: C 18Calculated for H6Br2O4 (M+H) = 445; found: 445. 1H NMR (400 MHz, TCE) δ 9.47 (dd, J = 8.4, 1.5 Hz, 1H), 8.76 (d, J = 14.2 Hz, 2H), 7.72-7.63 (m, 1H), 7.56 (dd, J = 8.3, 1.4 Hz, 1H), 7.46 (ddd, J = 8.5, 6.7, 1.9 Hz, 1H).

[0381] Compound PLC-52.2 (2-(4-(5,11-dibromo-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid): Compound PLC-52.2 was synthesized in a manner similar to the procedure described above from PLC-52.1 (7.000 mmol, 3.136 g), 2-(4-aminophenyl)acetic acid (14.00 mmol, 2.117 g), and DMAP (2.100 mmol, 257 mg) in anhydrous DMF (65 mL) at 160 °C. The crude reaction mixture was cooled to 0 °C, quenched with 6 N HCl (approximately 5 mL), and diluted with water (up to approximately 350 mL). The precipitate was filtered off and washed with water. The product was dried by suction and used in the next reaction without further purification. The yield is assumed to be 100%. MS(APCI):Chemical formula:C 26 H 13 Calculated for Br2NO5 (M+H) = 578; Found: 578.

[0382] Compound PLC-52.3 (2-(4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid): Compound PLC-52.3 was synthesized from compound PLC-52.2 (3.500 mmol, 2.034 g), (4-(trifluoromethyl)phenyl)boronic acid (14.00 mmol, 2.659 g), KCO (19.25 mmol, 2.661 g), and Pd(dppf)Cl (0.0245 mmol, 179 mg) in THF (60 mL), DMF (12 mL), and water (6 mL) by heating at 80 °C overnight under an argon atmosphere. The crude reaction mixture was evaporated to dryness in vacuo, dissolved in DCM, and evaporated in vacuo onto approximately 35 g of flash silica gel. Purification was achieved by flash chromatography on silica gel (220 g, equilibrated to 0% EtOAc / DCM, eluting from 0% (10 CV) to 15.3% EtOAc / DCM (15.3 CV) to 40% EtOAc / DCM (10 CV) to isocratic 40% EtOAc / DCM). The EtOAc contained 0.1% v / v TFA. The product-containing fractions were evaporated to dryness in vacuo to yield 2.000 g (80.3% from compound 80.1 (1655-11)) of a tan solid. MS (APCI): Formula: C 40 H 21 Calculated for F6NO5 (M+H) = 710; found: 710. 1H NMR (400 MHz, DMSO) δ 12.44 (s, 1H), 8.47 (s, 1H), 8.23 ​​(s, 1H), 8.02 (d, J = 8.1 Hz, 2H), 7.97–7.88 (m, 4H), 7.75 (d, J = 8.0 Hz, 2H), 7.49–7.37 (m, 3H), 7.31 (d, J = 8.2 Hz, 1H), 7.30–7.24 (m, 2H), 7.02–6.91 (m, 2H), 3.68 (s, 2H).

[0383] Compound PLC-52.4: To a solution of compound PLC-29 (113 mg, 0.1 mmol) in 8 mL of anhydrous DCM and 3 mL of DMF was added NBS (106 mg, 0.6 mmol). The mixture was heated at 60° C. overnight. The resulting mixture was diluted with 100 mL of DCM, washed with water (2×50 mL), loaded onto silica gel, and purified by flash chromatography using an eluent of DCM / EA (0% to 10% EA). The main peak was collected. The solvent was removed, triturated with methanol, filtered, and air-dried to give a reddish-brown solid (80 mg, 58% yield). LCMS (APCI-): C 66 H 38 Calculated for BBr3Cl2F5N3O5 (M-): 1364.98; Found: 1365.

[0384] Compound PLC-52.5: A mixture of compound PLC-52.4 (54 mg, 0.039 mmol), 4-n-butylphenylboronic acid (42 mg, 0.236 mmol), Pd(PPh3)4 (14 mg, 0.012 mmol), and potassium carbonate (32 mg, 0.236 mmol) in THF / DMF / water (10 mL / 2 mL / 1 mL) was degassed and heated at 80 °C for 6 h. The resulting mixture was diluted with 100 mL of DCM, dry-loaded onto silica gel, and purified by flash chromatography using an eluent of hexane / DCM (0% DCM to 50% DCM). The first major peak was collected, and the solvent was removed to give the desired product as a red solid (10 mg, 30% yield). LCMS (APCI-): C 53 H 49 Calculated for BClFNO: 848.33 (M); found: 848. H NMR (400 MHz, TCE) δ 8.02 (bs, 2H), 7.36-7.14 (m, 6H), 6.73 (m, 8H), 4.42 (s, 1H), 2.61 (bs, 4H), 2.39-2.31 (m, 4H), 1.86 (s, 8H), 1.37 (p, J = 7.6 Hz, 4H), 1.30-1.15 (m, 6H), 0.85 (t, J = 7.3 Hz, 6H).

[0385] Compound PLC-52: A mixture of compound PLC-52.5 (10 mg, 0.012 mmol), (2-(4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid) (16 mg, 0.022 mmol), DMAP / TsOH (5 mg, 0.017 mmol), and DIC (0.05 mL, 0.31 mmol) in 5 mL of anhydrous DCM was stirred at room temperature overnight. The resulting mixture was loaded onto silica gel and purified by flash chromatography using an eluent of hexane / DCM (0% DCM to 100% DCM). The main desired peak was collected, and after removal of the solvent and trituration with MeOH, a dark brown solid (10 mg, 54% yield) was obtained. LCMS (APCI-): C 93 H 68 Calculated for BCl2F8N3O5: 1539.45 (M-); Found: 1539. 1H NMR (400 MHz, TCE) δ 8.64 (s, 1H), 8.40 (s, 1H), 8.03 (s, 2H), 7.83 (d, J = 8.2 Hz, 2H), 7.81-7.74 (m, 4H), 7.59 (d, J = 8.0 Hz, 2H), 7.46 (d, J = 8.2 Hz, 2H), 7.39-7.17 (m, 11H), 7.02 (d, J =8.0Hz,1H), 6.95~6.50(m,10H), 3.78(s,2H), 2.62(s,4H), 2.41~2.30(m,4H) , 1.87(s,8H), 1.41(p,J=7.4Hz,4H), 1.32~1.21(m,4H), 0.87(t,J=7.3Hz,6H).

[0386] Synthesis of compound PLC-53 [ka]

[0387] Compound PLC-53.1 (9-(6-(2-amino-4-(tert-butyl)phenoxy)-2-(2-hydroxyethyl)-1H-benzo[de]isoquinoline-1,3(2H)-dione): Compound PLC-53.1 was synthesized in a manner similar to the procedure described above from compound PLC-26.2 (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. 2.777 g (78% yield) of a tan solid was obtained. MS (APCI): Chemical Formula: C 24 H 24 Calculated for N2O4 (M+H) = 405; found: 405. 1H NMR (400 MHz, TCE) δ 8.80 (dd, J = 8.4, 1.2 Hz, 1H), 8.67 (dd, J = 7.3, 1.2 Hz, 1H), 8.46 (d, J = 8.3 Hz, 1H), 7.84 (dd, J = 8.4, 7.3 Hz, 1H), 7.02 to 6.92 (m, 3H), 6.87 (dd, J = 8.4, 2.3 Hz, 1H), 4.42 (t, J = 5.2 Hz, 2H), 3.95 (t, J = 5.2 Hz, 2H), 3.74 (s, 2H), 2.39 (s, 1H), 1.35 (s, 9H).

[0388] Compound PLC-53.2 (9-(tert-butyl)-2-(2-hydroxyethyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione): Compound PLC-53.2 was synthesized in a manner similar to the procedure described above from compound PLC-53.1 (6.863 mmol, 2.776 g), NaNO (51.475 mmol, 3.552 g), concentrated HCl (34.317 mmol, 2.83 mL), and CuSO 5HO (46.67 mmol, 11.653 g). The crude product was approximately 10% acetate ester, which was cleaved with KCO as described above. The crude cleavage mixture was dissolved in acetone, evaporated onto approximately 20 g of silica gel, and placed in a loader. Purification was carried out by flash chromatography on silica gel (120 g, solids, equilibrated 0% EtOAc / DCM, eluted (2 CV) to 85% EtOAc / DCM (20 CV)). Fractions containing the product were evaporated to dryness in vacuo. 732 mg (27% yield) of a yellow solid was obtained. MS (APCI): Formula: C 24 H 21 Calculated for NO4 (M+H) = 388; Found: 388.

[0389] Compound PLC-53.3 (4-(2-(9-(tert-butyl)-1,3-dioxo-1H-xantheno[2,1,9-def]isoquinolin-2(3H)-yl)ethoxy)-2,6-dichlorobenzaldehyde): Compound PLC-53.2 (0.200 mmol, 78 mg) and 2,6-dichloro-4-hydroxybenzaldehyde (0.260 mmol, 50 mg) were added to a 40 mL screw-cap vial, followed by dry DCE (10 mL) and a stir bar. The reaction mixture was stirred at room temperature, and DEAD (0.300 mmol, 0.137 mL) and PPh (0.300 mmol, 79 mg) were added. The reaction mixture was stirred at room temperature for 60 minutes. Additional DEAD (0.100 mmol, 0.046 mL) and PPh3 (0.100 mmol, 26 mg) were added and stirring was continued overnight at room temperature. The crude reaction mixture was loaded onto approximately 20 g of silica gel in a loader. Purification was carried out by flash chromatography on silica gel (80 g, solids, equilibrated 0% EtOAc / DCM, eluted 0% (2 CV) to 10% EtOAc / DCM (15 CV)). MS (APCI): Formula: C 31 H 23 Calculated for Cl2NO5 (M+H) = 560; Found: 560. 1H NMR (400 MHz, TCE) δ 10.36(s,1H), 8.66(d,J=7.9Hz,1H), 8.60(d,J=8.5Hz,1H), 8.06(d,J=2.3Hz,1H), 8.01(d,J=8.0Hz,1H), 7.63(dd,J=8.7,2.2Hz,1H), 7.3 7(d,J=8.8Hz,1H), 7.34(d,J=8.4Hz,1H), 6.99(s,2H), 6.95(d,J=14.5Hz,1H), 4.64(t,J=6.2Hz,2H), 4.39(t,J=6.2Hz,2H), 1.44(s,9H).

[0390] Compound PLC-53 (9-(tert-butyl)-2-(2-(4-(19,19-difluoro-6,7,11,12,13,19-hexahydro-5H-18|4,19|4-benzo[3',4']cyclohepta[1',2':4,5]pyrrolo[1,2-c]benzo[3',4']cyclohepta[1',2':4,5]pyrrolo[2,1-f][1,3,2]diazaborin-9-yl)-3,5-dimethylphenoxy)ethyl)-1H-xantheno[2,1,9-def]isoquinoline-1,3(2H)-dione): Compound PLC-53 was synthesized by the method of claim 1, Compound 53.3 was synthesized in a similar manner to 32 from compound 53.3 (0.186 mmol, 104 mg), 1,4,5,6-tetrahydrobenzo[6,7]cyclohepta[1,2-b]pyrrole (Ex-7.3, 0.371 mmol, 68 mg), and pTsOH·HO (0.0186 mmol, 3.5 mg) in dry DCM (20 mL) at room temperature and then at 50 °C, followed by DDQ (0.241 mmol, 55 mg), 2×EtN (1.485 mmol, 0.210 mL), and BF·OEt (2.227 mmol, 0.280 mL). The crude reaction mixture was diluted with hexane and then loaded onto approximately 20 g of silica gel in a loader. Purification was carried out by flash chromatography on silica gel (80 g, solids, equilibrated with 0% EtOAc / hexane, eluted with 0% (2 CV) to 75% EtOAc / hexane (30 CV)). Fractions containing the product were evaporated to dryness in vacuo. The crude product was triturated and dried in vacuo. 138 mg (78% yield) of a deep red solid was obtained. MS (APCI): Formula: C 59 H 50 Calculated for BF2N3O4 (M+H) = 954; Found: 954. 1H NMR (400 MHz, TCE) δ 8.70(d,J=7.9Hz,1H), 8.64(d,J=8.4Hz,1H), 8.10~7.99(m,4H), 7.63(dd,J=8.7,2.2Hz,1H), 7.42~7.32(m,6H), 7.32~7.24(m,2H), 7.1 4(s,2H), 6.43(s,2H), 4.70(t,J=6.2Hz,2H), 4.42(t,J=6.3Hz,2H), 2.62(t,J=6.6Hz,4H), 2.30(s,4H), 2.11~1.96(m,4H), 1.44(s,9H).

[0391] Example 10 - Preparation of filter layer The glass substrates were prepared essentially as follows: 1.1 mm thick glass substrates measuring 1 inch by 1 inch were cut to size. The glass substrates were then cleaned with detergent and deionized (DI) water, rinsed with fresh DI water, and sonicated for approximately 1 hour. The glass was then immersed in isopropanol (IPA) and sonicated for approximately 1 hour. The glass substrates were then immersed in acetone and sonicated for approximately 1 hour. The glass was then removed from the acetone bath and dried with nitrogen gas at room temperature.

[0392] A 20 wt% solution of poly(methyl methacrylate) (PMMA) copolymer (average molecular weight 120,000 by GPC, MilliporeSigma, Burlington, Massachusetts, USA) in cyclopentanone (99.9% purity) was prepared. The copolymer was stirred overnight at 40°C. (PMMA) CAS: 9011-14-7, (cyclopentanone) CAS: 120-92-3.

[0393] The 20% PMMA solution (4 g) prepared above was added to 3 mg of the photoluminescent complex prepared above in a sealed container and mixed for approximately 30 minutes. The PMMA / luminophore solution was then spin-coated onto the prepared glass substrate at 1000 RPM for 20 seconds followed by 500 RPM for 5 seconds. The resulting wet coating had a thickness of approximately 10 μm. The sample was covered with aluminum foil before spin-coating to protect it from light exposure. Three samples were prepared in this manner for each of the emission / FWHM and quantum yield measurements. The spin-coated samples were baked in a vacuum oven at 80°C for 3 hours to evaporate the remaining solvent.

[0394] A 1 inch x 1 inch sample was inserted into a Shimadzu 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 PLC-1 are shown in Figure 1, those obtained for PLC-2 are shown in Figure 2, and those obtained for PLC-3 are shown in Figure 3.

[0395] The fluorescence spectra of 1" x 1" film samples prepared as described above were determined using a Fluorolog spectrofluorometer (Horiba Scientific, Edison, NJ, USA) with excitation wavelengths set at their respective maximum absorbance wavelengths. The emission maxima and FWHM are shown in Table 1.

[0396] The quantum yields of 1 inch × 1 inch samples prepared as described above were determined using a Quantarus-QY spectrophotometer (Hamamatsu Inc., Campbell, CA, USA) with excitation at their respective maximum absorption wavelengths. The results are reported in Table 1.

[0397] The film characterization results (absorbance peak wavelength, FWHM, and quantum yield) are shown in Table 1 below.

[0398] [Table 1] [Table 2] [Table 3] [Table 4] [Table 5] Table 6 Table 7 Table 8 Table 9 Table 10 Table 11 Table 12 Table 13 Table 14 Table 15 Table 16 Table 17 Table 18 Table 19 Table 20

Claims

1. A photoluminescent complex comprising: a blue-light absorbing donor chromophore comprising a naphthalimide derivative; a linker complex; a ring-locked boron dipyrromethene (BODIPY) moiety; Including, the linker conjugate covalently bonds the donor chromophore having the naphthalimide derivative to the ring-locked BODIPY moiety, the naphthalimide derivative absorbs blue light energy at a first excitation wavelength and transfers the energy to the ring-locked BODIPY moiety, and the ring-locked BODIPY moiety emits light energy at a second, longer wavelength, and the photoluminescent complex has an emission quantum yield of greater than 80%; The photoluminescent complex has the general formula: 【Chemistry 1】 wherein R 1 and R 2 are independently H, C 1 -C 3 alkyl, or a substituted aryl group; R 3 and R 4 are independently H, F, Br, or —CF 3 ; R 5 and R 6 are independently H, C 1 -C 3 alkyl, halide, or C 1 -C 3 alkoxy; each X is independently a C 1 -C 3 alkyl group or a spirocycloalkane group; L is a linker conjugate; and Z is a donor chromophore, and Z is of the general formula: 【Chemistry 2】 wherein Y is O or S, R 7 and R 8 are independently H, substituted or unsubstituted aryl, or —CF 3 , and R 9 is independently H, substituted or unsubstituted aryl, or C 1 -C 5 alkyl; The linker conjugate is an unsubstituted ester, the unsubstituted ester having the following structure: 【Transformation 3】 including one of: The linker conjugate is a substituted ester, the substituted ester having the following structure: 【Chemistry 4】 including one of: The linker conjugate is an unsubstituted and / or substituted ether, and the unsubstituted and / or substituted ether has the following structure: 【Transformation 5】 including one of: Photoluminescent complexes.

2. The photoluminescent complex has the following structure: 【Transformation 6】 【Transformation 7】 【Transformation 8】 【Chemistry 9】 【Chemistry 10】 【Chemistry 11】 【Chemistry 12】 【Chemistry 13】 【Chemistry 14】 【Chemistry 15】 【Chemistry 16】 【Chemistry 17】 [Chemistry 18] 【Chemistry 19】 【Chemistry 20】 【Chemistry 21】 【Chemistry 22】 【Chemistry 23】 【Chemistry 24】 【Chemistry 25】 【Chemistry 26】 【Chemistry 27】 【Chemistry 28】 【Chemistry 29】 【Transformation 30】 【Chemistry 31】 【Chemistry 32】 10. The photoluminescent complex of claim 1, comprising one of:

3. A color conversion film, A transparent substrate layer; a color conversion layer including a resin matrix; at least one photoluminescent complex according to claim 1 or 2 dispersed within the resin matrix; Including color conversion film.

4. The color conversion film of claim 3 , further comprising a singlet oxygen quencher.

5. The color conversion film of claim 3 further comprising a free radical scavenger.

6. 4. The color conversion film of claim 3, wherein the film has a thickness between 10 μm and 200 μm.

7. 4. The color conversion film of claim 3, wherein the film absorbs light in the wavelength range of 400 nm to 480 nm and emits light in the wavelength range of 590 nm to 650 nm.

8. A method for making a color conversion film, comprising: Dissolving the photoluminescent complex according to claim 1 or 2 and a binder resin in a solvent; applying the mixture to a transparent substrate layer; A method comprising:

9. A backlight unit comprising the color conversion film according to any one of claims 3 to 7.

10. A display device comprising the backlight unit according to claim 9.

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