TW202330556A - Boron-containing cyclic emissive compounds and color conversion film containing the same - Google Patents

Abstract

The present disclosure relates to novel photoluminescent complexes comprising a BODIPY moiety, a blue light absorbing moiety, and a linker complex, wherein the linker complex covalently bonds the blue light absorbing moiety to the ring-locked BODIPY moiety, a color conversion film comprising the photoluminescent complex, and a back-light unit using the same.

Description

Boron-containing cyclic light-emitting compound and color conversion film containing the boron-containing cyclic light-emitting compound

Unless otherwise indicated herein, 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.

In color reproduction, a gamut or gamut is some complete subset of the colors available on a device such as a television or monitor. For example, Adobe ^™ red-green-blue (RGB) was developed to provide a wider color gamut and a more realistic representation of visible colors viewed through a display through a wide-gamut color space achieved by using pure spectral primaries. It is believed that devices that provide a wider gamut will enable displays to depict more vivid colors.

As high-definition large-screen displays have become more common, the demand for higher performance, more compact and highly functional displays has increased. Currently light emitting diodes (LEDs) are obtained by a blue light source that excites a green phosphor, a red phosphor or a yellow phosphor to obtain a white light source. However, the full-width-half-maximum (FWHM) of the emission peaks of current blue and red phosphors is very large, typically greater than 40 nm, causing the green and red spectra to overlap and rendering the colors not sufficiently distinguishable from each other. This overlap results in poor color rendering and degradation of color gamut.

To correct the degradation of color gamut, methods have been developed using films containing quantum dots in combination with LEDs. However, quantum dots suffer from various disadvantages, including toxicity, low efficiency, expensive packaging process, and dimensional uniformity.

Therefore, there is a need to improve the performance of color conversion films, backlight units and display devices.

The photoluminescent composites described herein can be used to increase the contrast between distinguishable colors in televisions, computer monitors, smart devices, and any other device that utilizes a color display. The photoluminescent complex of the present invention comprises a color conversion dye complex with good blue light absorbance and narrow emission bandwidth, wherein the full half width maximum [FWHM] of the emission band is less than 40 nm. In some embodiments, the photoluminescent composite absorbs light at a first wavelength and emits light at a second wavelength longer than the first wavelength. The photoluminescent composites disclosed herein can be used with color conversion films for light emitting devices. The color conversion film of the present invention reduces color degradation by reducing overlap within the color spectrum, resulting in high quality color rendering.

Some embodiments comprise photoluminescent complexes, wherein the photoluminescent complexes may comprise: blue light absorbing naphthyl imide derivatives; including unsubstituted esters, substituted esters, unsubstituted ethers or substituted a linker complex of ethers; and a ring-locked boron-dipyrromethene (BODIPY) moiety. In some embodiments, the linker complex can covalently link the naphthylimide derivative to the ring-locked BODIPY moiety. In many embodiments, the ring-locked BODIPY moiety absorbs energy from a first excitation wavelength of the naphthylimide derivative and emits light energy at a second, higher wavelength. In various embodiments, the photoluminescent composite has an emission quantum yield greater than 80%.

In some embodiments, the photoluminescent composite can have an emission band with a full width half width maximum [FWHM] of at most 40 nm.

In many embodiments, the photoluminescent complex can have a Stokes shift equal to or greater than 45 nm, the difference between the excitation peak of the blue light absorbing moiety and the emission peak of the BODIPY moiety.

Many embodiments include a color converting film, wherein the color converting film may comprise: a transparent substrate layer; a color converting layer, wherein the color converting layer comprises a resin matrix; and at least one light as described herein dispersed within the resin matrix Luminescent compound. In some embodiments, the color conversion film may have a thickness of 1 μm to about 200 μm. In many embodiments, the color conversion films of the present invention can absorb blue light in the range of 400 nm to about 480 nm and emit light in the wavelength range of 510 nm to about 560 nm. Another embodiment includes a color conversion film that absorbs blue light in the range of 400 nm to about 480 nm and emits 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 include two opposing surfaces, wherein the color converting layer is disposed on one of the opposing surfaces.

In some embodiments, the color conversion film may further include a singlet oxygen quencher. In some embodiments, the color conversion film may further include a free radical scavenger.

Many embodiments include a method of making a color conversion film, the method comprising: dissolving a photoluminescent composite as described herein and a binder resin in a solvent; and applying the mixture to opposing surfaces of a transparent substrate One of them goes up.

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

Some embodiments include display devices that include the backlight units described herein.

The present application provides a photoluminescent composite having excellent color gamut and luminous properties; a method of manufacturing a color conversion film using the photoluminescent composite, and a backlight unit including the color conversion film. These and other embodiments are described in more detail below.

The present invention relates to a photoluminescent composite for a color conversion film, a backlight unit and a display device comprising the backlight unit. Photoluminescent composites can be used to increase and enhance the transmission of one or more desired emission bandwidths within the color conversion film. In some embodiments, the photoluminescent composite can both enhance transmission of a desired first emission bandwidth and reduce transmission of a second emission bandwidth. In some embodiments, the present disclosure describes photoluminescent composites that can enhance the contrast or intensity between two colors, increasing their differentiation from each other.

In some embodiments, boron-dipyrromethene (BODIPY) compounds are used as emissive materials instead of quantum dots. BODIPY complexes can have narrow FWHMs, high fluorescence efficiency, stability to both moisture and oxygen, and low production costs. Current BODPY strategies have some disadvantages, such as low absorption of blue LED light, eg, 450 nm, which results in inefficient conversion of blue LED light to green and red light, and wide FWHM when used in color conversion films. In some embodiments, the BODIPY compounds disclosed herein overcome these limitations.

As used herein, when a compound or chemical structure is referred to as being "substituted," the compound or structure may contain one or more substituents. A substituted group is derived from an unsubstituted parent structure wherein one or more hydrogen atoms on the parent structure are independently replaced by one or more substituents. In some embodiments, the substituents can be independently F, Cl, Br, I, C _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 ₃ alkyl, C ₄ alkyl, etc., fluoroalkyl, for example, CF ₃ , etc.) , alkenyl or C _3-7 heteroalkyl.

As used herein, the term "alkyl" refers to a hydrocarbon group that does not contain carbon-carbon double or triple bonds, and that includes linear, branched or cyclic alkyl groups.

An "olefinic" moiety refers to a group having at least one carbon-carbon double bond (-C=C-) and comprising a linear, branched or cyclic olefinic moiety.

An "alkyne" moiety refers to a group having at least one carbon-carbon triple bond (-C≡C-) and comprising a linear, branched or cyclic alkyne moiety.

In some embodiments, the alkyl moiety may have from 1 to 6 carbon atoms (whether or not they appear herein), numerical ranges such as "1 to 6" refer to each integer within the given range: for example, " 1 to 6 carbon atoms" means an alkyl group which may have 1 carbon atom, 2 carbon atoms, 3 carbon atoms, etc., up to and including 6 carbon atoms, although this definition also covers occurrences of the term "alkyl" , where no range of numbers is specified. Alkyl groups of compounds designated herein may be designated as "C _1-6 alkyl" or similar designations. By way of example only, "C _1-6 alkyl" indicates the presence of 1 to 6 carbon atoms in the alkyl chain, i.e., the alkyl chain is methyl, ethyl, propyl, isopropyl, n-butyl , isobutyl, second butyl or third butyl, etc. Thus, C _1-6 alkyl includes, for example, C _1-2 alkyl, C _3-4 alkyl, C _4-5 alkyl or C _5-6 alkyl. Alkyl groups can be substituted or unsubstituted. Typical alkyl groups include (but are by no means limited to): methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, vinyl, propenyl, butenyl , cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.

Typical alkenyl groups include, but are not limited to, ethenyl, propenyl, butenyl, and the like.

As used herein, the term "heteroalkyl" refers to an alkyl group as defined herein in which one or more of the constituent carbon and/or hydrogen atoms have been replaced by nitrogen, oxygen or sulfur. Examples include, but are not limited to, -CH ₂ -O-CH ₃ , -CH ₂ -CH ₂ -O-CH ₃ , -CH ₂ -N(CH ₃ )-CH ₃ , -CH ₂ -CH ₂ -NH- CH ₃ , -CH ₂ -CH ₂ -N(CH ₃ )-CH ₃ , -CH ₂ -S-CH ₂ -CH ₃ , -CH ₂ -NH-O-CH ₃ , etc.

The term "aromatic" refers to a planar ring having a delocalized π-electron system containing 4n+2 π electrons, where n is an integer. Aromatic rings can be formed from five, six, seven, eight, nine or more than nine atoms. Aromatic rings can be optionally substituted. The term "aromatic" includes both carbocyclic aryl (eg, phenyl) and heterocyclic aryl (or "heteroaryl" or "heteroaromatic") groups (eg, pyridine). The term includes monocyclic or fused-ring polycyclic (ie, rings that share adjacent pairs of carbon atoms) groups.

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

Illustrative examples of polycyclic groups include the following moieties: [bicyclooctane], [Dicyclopentane], [bicycloheptane], [bicycloheptane], [bicyclodecane], [decalin], [octahydropentene], [octahydroindene], [hexahydroindene], [1,2,3,4-tetrahydronaphthalene], [2,3-dihydro-1 H -indene], [2',3'-Dihydrospiro[cyclopentane-1,1'-indene] or [1,2,3,3a-Tetrahydropentene].

As used herein, the term "aryl" means an aromatic ring wherein each of the atoms forming the ring is a carbon atom. Aryl rings can be formed by five, six, seven, eight or more than eight carbon atoms. Aryl groups can be substituted or unsubstituted. Examples of aryl groups include, but are not limited to, phenyl, naphthyl, phenanthrenyl, and the like.

The term "heteroaryl" refers to an aryl group containing one or more ring heteroatoms selected from nitrogen, oxygen, sulfur, or combinations thereof, wherein the heteroaryl has 4 to 10 atoms in its ring system with the proviso that The ring of this group does not contain two adjacent nitrogen, oxygen or sulfur atoms. It is understood that heteroaryl rings may have additional heteroatoms in the ring. In a heteroaryl group having two or more heteroatoms, those two or more heteroatoms may be the same or different from each other. Heteroaryl groups 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 include the moieties: pyrrole, imidazole, and the like.

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

As used herein, the terms "bond", "bond", "direct bond" or "single bond" mean a chemical bond between two atoms.

As used herein, the term "moiety" refers to a specific part or functional group of a molecule. Chemical moieties are generally recognized as chemical entities embedded or attached to molecules.

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

The term "ester" refers to a chemical moiety having the formula -COOR, where R is alkyl, cycloalkyl, aryl, heteroaryl (bonded through a ring carbon), or heterocycle (bonded through a ring carbon). Any hydroxyl or carboxyl side chains on the compounds described herein may be esterified. Procedures and specific groups for preparing such esters can be by any suitable method and can be readily found in reference sources.

As used herein, the term "ether" refers to a chemical moiety having the general formula R-O-R' containing an oxygen atom attached to two alkyl or aryl groups, wherein the terms alkyl and aryl are as defined herein .

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

As used herein, the term "ring-locked" refers to a chemical structure in which one or more series of atoms in a compound are linked to form a ring. Rings can vary in size from three to many atoms (eg, aromatic rings, carbocyclic rings).

As used herein, the term "BODIPY" refers to a chemical moiety having the formula: .

BODIPY may consist of dipyrromethane complexed with a disubstituted boron atom, typically a _BF2 unit. The IUPAC name of BODIPY is 4,4-difluoro-4-bora-3a,4a-diaza-s-dicyclopentadieneindacene.

As used herein, the term "naphthyl imide" or "naphthyl imide derivative" refers to a chemical moiety having the formula: .

The present invention relates to photoluminescent composites that absorb light energy at a first wavelength and emit light energy at a second, higher wavelength. The photoluminescent complex of the present invention comprises an absorbing luminescent moiety and an emitting luminescent moiety coupled through a linker such that its distance is adjusted for the absorbing luminescent moiety to transfer its energy to the acceptor luminescent moiety, wherein the acceptor luminescent moiety then reacts at a greater than the absorbing luminescent moiety. The first wavelength is emitted at the second wavelength.

Some embodiments comprise photoluminescent complexes. In some examples, the complex comprises: a blue light-absorbing donor chromophore (wherein the donor chromophore comprises a naphthylimide derivative), a linker complex, and a ring-locked boron-dipyrromethane (BODIPY )part. In some embodiments, the linker complex can covalently link the naphthylimide derivative to the ring-locked BODIPY moiety. In some examples, the naphthyl imide derivative absorbs light at a first excitation wavelength and transfers energy to a ring-locked BODIPY moiety, wherein the ring-locked BODIPY moiety then emits light energy at a second wavelength. It is believed that energy transfer from the excited naphthyl imide derivative to the ring-locked BODIPY moiety occurs via Förster resonance energy transfer (FRET). This is believed to be due to the absorption/emission spectrum of the photoluminescent complex, in which there are two main absorption bands, one on the blue light absorption band (naphthalimide derivative) and one on the ring-locked BODIPY absorption band, and only one emission band bit at the emission wavelength of the BODIPY portion (see Figures 1 and 2 ).

In one embodiment, the photoluminescent composite can 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%, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 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 can have an emission quantum yield of greater than 80%. In some embodiments, the quantum yield can 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 can go up to almost 100%. Quantum measurements of films can be performed by a spectrophotometer, eg, Quantaurus-QY spectrophotometer (Hamamatsu, Inc., Campbell, CA, USA).

In some embodiments, the photoluminescent composite has an emission band, wherein the emission band can have a full width half width maximum (FWHM) of less than 40 nm. FWHM is the width of the emission band at an emission intensity half of the maximum emission intensity of the emission band, in nanometers. In some embodiments, the photoluminescent composite has an emission band FWHM value of less than or equal to about 35 nm, less than or equal to about 30 nm, less than or equal to about 25 nm, or less than or equal to about 20 nm. In some embodiments, the 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.

In some embodiments, the photoluminescent composite can have a Stokes shift equal to or greater than 45 nm. As used herein, the term "Stokes shift" means the distance between the excitation peak of the blue light absorbing moiety and the emission peak of the BODIPY moiety. In some embodiments, the Stokes shift is at least 45 nm. In some embodiments, the Stokes shift of the photoluminescent complex can be about 45 to 50 nm, about 50 to 55 nm, about 55 to 60 nm, about 60 to 65 nm, about 65 to 70 nm, about 70 to 75 nm, about 75 to 80 nm, about 80 to 85 nm, about 85 to 90 nm, about 90 to 95 nm, about 95 to 100 nm, or greater than about 100 nm, or any of these equivalents Any value within the bounds of those constraints.

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

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

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 to 600 nm, about 600 to 605 nm, about 605 to 610 nm, about 610 to 615 nm, about 615 to 620 nm, Between about 620 to 625 nm, about 625 to 630 nm, about 630 to 635 nm, about 635 to 640 nm, about 640 to 645 nm, about 645 to 650 nm, about 650 to 655 nm, about 655 to 660 nm, or any wavelength within the range bounded by any of these equivalents.

Other embodiments include photoluminescent complexes in which the spatial distance between the blue light-absorbing naphthyl imide derivative and the BODIPY moiety is adjusted through a linker complex for the transfer of energy from the blue light absorbing naphthyl imide derivative to the BODIPY moiety transfer.

The present invention describes a photoluminescent complex (PLC) comprising a blue-light absorbing naphthyl imide derivative, a linker complex, and a ring-locked BODIPY moiety. The linker complex covalently links the blue light absorbing naphthyl imide derivative and the ring-locked BODIPY moiety. In some embodiments, the naphthyl imide derivative absorbs light energy at the first excitation wavelength and transfers the energy to a ring-locked BODIPY moiety, wherein the ring-locked BODIPY moiety absorbs energy from the naphthyl imide derivative and Light energy of a second higher wavelength is emitted. In these embodiments, the photoluminescent composite has an emission quantum yield greater than 80%.

This linker complex covalently links the blue light absorbing naphthyl imide derivative to the ring-locked BODIPY moiety. This linker complex can be tuned to adjust the spatial distance of the blue light absorbing naphthyl imide derivative and the ring-locked BODIPY moiety. The quantum yield can be tuned by adjusting the spatial distance between the ring-locked naphthyl imide derivative and the ring-locked BODIPY. In some embodiments, the distance separating the blue-absorbing naphthimide derivative and the ring-locked BODIPY moiety can be about 8 Å or less. This linker complex maintains the distance between the blue-light absorbing naphthyl imide derivative and the ring-locked BODIPY moiety.

In some embodiments, the photoluminescent complex comprises a linker complex (L), wherein the linker complex covalently links the blue light absorbing naphthyl imide derivative to the ring-locked BODIPY moiety. In some embodiments, the linker complex can include a single bond between the naphthylimide derivative and the ring-locked BODIPY moiety.

In some embodiments, the linker complex can include unsubstituted esters, substituted esters, unsubstituted ethers, or substituted ethers. In some embodiments, the linker complex can include optionally substituted _C2-7 ester groups.

Some examples include linker complexes comprising substituted ester groups, wherein the linker complexes can be selected from one of the following structures: , or .

In some embodiments, the linker complex can comprise unsubstituted ester groups. When the linker complex comprises an unsubstituted ester group, the linker complex comprises one of the following structures:

In some embodiments, the linker complex can comprise unsubstituted and/or substituted ethers. When the linker complex comprises unsubstituted and/or substituted ethers, the linker complex comprises one of the following structures:

The photoluminescent complexes of the present invention may comprise a ring-locked BODIPY moiety. The BODIPY portion of the ring lock may have the general formula: . In some embodiments, R ₁ and R ₂ can be H or C _1-3 alkyl. In some embodiments, R _{and R} can be substituted aryl moieties, wherein the substituents on the aryl moiety can be C _1-6 alkyl. In some embodiments, R ₃ and R ₄ can be H, F, Br or -CF ₃ . In some embodiments, R ₅ and R ₆ can be H, halide (eg, -F, -Cl and/or -Br), C ₁ -C ₃ alkyl (eg, -CH ₃ ), C ₁ - C ₃ alkoxy (eg, -OCH ₃ ). In some embodiments, X can be C ₁ -C ₃ alkyl, for example, -CH ₂ -, -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, or spirocycloalkyl.

In some embodiments, R ₁ is H.

In some embodiments, R ₁ is C _1-3 alkyl.

In some embodiments, R ₂ is H.

In some embodiments, R ₂ is C _1-3 alkyl.

In some embodiments, R ₁ and R ₂ are H.

In some embodiments, R ₁ and R ₂ are C _1-3 alkyl.

In some embodiments, R ₁ is a substituted aryl moiety, eg, phenyl, wherein the substituent on the aryl moiety (eg, phenyl) can be C _1-6 alkyl.

In some embodiments, _R is a substituted aryl moiety, eg, phenyl, wherein the substituent on the aryl moiety (eg, phenyl) can be C _1-6 alkyl.

In some embodiments, R _{and R} are substituted aryl moieties, eg, phenyl, wherein the substituents on the aryl moiety (eg, phenyl) can be C _1-6 alkyl.

In some embodiments, R ₃ is H.

In some embodiments, R ₃ is F.

In some embodiments, R ₃ is Br.

In some embodiments, R ₃ is -CF ₃ .

In some embodiments, _R4 is H.

In some embodiments, R ₄ is F.

In some embodiments, R ₄ is Br.

In some embodiments, R ₄ is -CF ₃ .

In some embodiments, _R3 and _R4 are H.

In some embodiments, _R3 and _R4 are F.

In some embodiments, R ₃ and R ₄ are Br.

In some embodiments, R ₃ and R ₄ are -CF ₃ .

In some embodiments, R ₅ is H.

In some embodiments, R ₅ is -F.

In some embodiments, R ₅ is -Cl.

In some embodiments, R ₅ is -Br.

In some embodiments, R ₅ is C ₁ -C ₃ alkyl.

In some embodiments, R ₅ is -CH ₃ .

In some embodiments, R ₅ is C ₁ -C ₃ alkoxy.

In some embodiments, R ₅ is -OCH ₃ .

In some embodiments, R ₆ is H.

In some embodiments, R ₆ is -F.

In some embodiments, R ₆ is -Cl.

In some embodiments, R ₆ is -Br.

In some embodiments, R ₆ is C ₁ -C ₃ alkyl.

In some embodiments, R ₆ is -CH ₃ .

In some embodiments, R ₆ is C ₁ -C ₃ alkoxy.

In some embodiments, R ₆ is -OCH ₃ .

In some embodiments, R ₅ and R ₆ are H.

In some embodiments, _R5 and _R6 are -F.

In some embodiments, _R5 and _R6 are -Cl.

In some embodiments, R ₅ and R ₆ are -Br.

In some embodiments, R ₅ and R ₆ are C ₁ -C ₃ alkyl.

In some embodiments, R ₅ and R ₆ are -CH ₃ .

In some embodiments, R ₅ and R ₆ are C ₁ -C ₃ alkoxy.

In some embodiments, R ₅ and R ₆ are -OCH ₃ .

In some embodiments, R ₅ and R ₆ can be H, —CH ₃ , Cl, F, or OCH ₃ .

In some embodiments, X is C ₁ -C ₃ alkyl.

In some embodiments, X is -CH ₂ .

In some embodiments, X is -CH ₂ CH ₂ -.

In some embodiments, X is -CH ₂ CH ₂ CH ₂ -.

In some embodiments, X is spirocycloalkyl.

In some embodiments, L is an unsubstituted ester.

In some embodiments, L is a substituted ester.

In some embodiments, L is an unsubstituted ether.

In some embodiments, L is a substituted ether.

Many embodiments comprise blue light absorbing naphthyl imide derivatives (Z), wherein the blue light absorbing naphthyl imide derivatives may have the following general formula: , where Y can be oxygen (O) or sulfur (S). In some embodiments, R ₇ and/or R ₈ can be hydrogen (H), substituted or unsubstituted aryl, or -CF ₃ . In some embodiments, R ₉ can be H, substituted or unsubstituted aryl, C _1-5 alkylaryl, _substituted or unsubstituted aryl carboxylic acid (such as for CO ₂ -third Butyl-phenyl), or there is no substitution for _R9 .

In some embodiments, Y is oxygen (O).

In some embodiments, Y is sulfur (S).

In some embodiments, R ₇ is H.

In some embodiments, R ₇ is substituted aryl.

In some embodiments, R ₇ is unsubstituted aryl.

In some embodiments, R ₇ is -CF ₃ .

In some embodiments, R ₈ is H.

In some embodiments, R ₈ is substituted aryl.

In some embodiments, R ₈ is unsubstituted aryl.

In some embodiments, R ₈ is -CF ₃ .

In some embodiments, _R7 and _R8 are H.

In some embodiments, _R7 and _R8 are substituted aryl.

In some embodiments, _R7 and _R8 are unsubstituted aryl.

In some embodiments, R ₇ and R ₈ are -CF ₃ .

In some embodiments, _R9 is H.

In some embodiments, R ₉ is substituted aryl.

In some embodiments, R ₉ is unsubstituted aryl.

In some embodiments, R ₉ is C _1-5 alkylaryl _.

In some embodiments, R ₉ is a substituted arylcarboxylic acid.

In some embodiments, R ₉ is an unsubstituted arylcarboxylic acid.

In some embodiments, R ₉ is p-CO ₂ -tert-butyl-phenyl.

The photoluminescent complexes of the present invention can be represented by the following structures, which are provided for illustrative purposes only and should in no way be construed as limiting: , or a combination thereof.

In some embodiments, the photoluminescent compound comprises a blue light absorbing naphthyl imide derivative. In some examples, the blue light-absorbing naphthyl imide derivative may include an organic luminescent group. In many embodiments, the blue light absorbing moiety can have a peak absorption maximum between a wavelength of about 400 nm to 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, and 460 nm, 470 nm, or 480 nm. In many embodiments, the photoluminescent complex can have a peak absorption maximum at about 450 nm. In some embodiments, the blue light-absorbing naphthyl imide derivative may have a maximum peak absorption at about 410 nm and a lowest maximum peak absorption at about 400 nm. Still in many embodiments, the blue light absorbing naphthyl imide derivative can have a maximum peak absorption at about 480 nm.

Some embodiments include a color conversion film, wherein the color conversion film comprises: a color conversion layer, wherein the color conversion layer comprises a resin matrix and the aforementioned photoluminescent composite dispersed within the resin matrix. In many embodiments, the color conversion film can comprise one or more of the photoluminescent composites described herein.

Some embodiments include a color conversion film, which can be from about 1 μm to about 200 μm thick. In many embodiments, the color conversion film can be described as about 1 µm to about 5 µm thick, about 5 µm to about 10 µm thick, about 10 µm to about 15 µm thick, about 15 µm to about 20 µm thick, About 20 µm to about 40 µm thick, about 40 µm to about 80 µm thick, about 80 µm to about 120 µm thick, about 120 µm to about 160 µm thick, about 160 µm to about 200 µm thick, or bound by the above range of any thickness.

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

In some embodiments, the color conversion film may further include a transparent substrate layer. The transparent substrate layer has two opposing surfaces, wherein the color conversion layer can be disposed on and in physical contact with the surface of the transparent layer adjacent to the light emitting source. The transparent substrate is not particularly limited and those skilled in the art can select the 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 (polyethylene terephthalate modified with ethylene glycol) glycol ester), PDMS (polydimethylsiloxane), COC (cycloolefin copolymer), PGA (polyglycolic acid or polyglycolic acid), PLA (polylactic acid), PCL (polycaprolactone) , PEA (polyethylene adipate), PHA (polyhydroxyalkanoate), PHBV (poly(3-hydroxybutyrate copolymer 3-hydroxyvalerate)), PBE (polybutylene terephthalate glycol esters), PTT (polytrimethylene terephthalate). Any of the above-mentioned resins may be the corresponding respective monomers and/or polymers.

In some embodiments, the transparent substrate may have two opposite surfaces. In many embodiments, the color converting film can be disposed on and in physical contact with one of the opposing surfaces. In some embodiments, the side of the transparent substrate on which the color conversion film is not disposed may be adjacent to the light source. The substrate can function as a support during the preparation of the material for the color conversion film. The type of substrate used is not particularly limited, and the material and/or thickness are not limited as long as it is transparent and functions as a support. Those skilled in the art can determine which material and thickness to use for the support substrate.

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

Binder resins that can be used with the photoluminescent composite(s) include resins such as acrylic resins, polycarbonate resins, ethylene-vinyl alcohol copolymer resins, ethylene-vinyl acetate copolymer resins, and saponified products thereof , AS resin, polyester resin, vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral resin, polyvinyl phosphonic acid (PVPA), polystyrene resin, phenolic resin, phenoxy resin, polystyrene, Nylon, cellulose resin and cellulose acetate resin. In some embodiments, the binder resin may be polyester resin and/or acrylic resin.

Solvents that can be used to dissolve or disperse the compound and resin can include alkanes such as butane, pentane, hexane, heptane, and octane; cycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane ; Alcohols, such as ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, decyl alcohol, undecyl alcohol, diacetone alcohol and furyl alcohol; Cellosolves ^TM , such as methyl Cellosolve ^TM , ethyl Cellosolve ^TM , Butyl Cellosolve ^TM , Methyl Cellosolve ^TM Acetate and Ethyl Cellosolve ^TM Acetate; Propylene Glycol and its derivatives such as Propylene Glycol Monomethyl Ether, Propylene Glycol Monoethyl Ether 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, acetic acid Amyl Butyrate, Butyl Butyrate, Diethyl Oxalate, Ethyl Pyruvate, Ethyl 2-Hydroxybutyrate, Ethyl Acetate, Methyl Lactate, Ethyl Lactate and 3-Methoxy methyl propionate; 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, dimethyl Acetamide and N-methylpyrrolidone.

Some embodiments include a backlight unit. In some examples, the backlight unit may comprise the above-mentioned color conversion film comprising the photoluminescent composite(s) described herein.

Other embodiments may include a display device, where the device may include a backlight unit as described herein.

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

For the disclosed processes and/or methods, the functions performed in the processes and methods may be performed in a different order, as may be dictated by the context. Furthermore, the steps and operations outlined are provided as examples only and some of these steps and operations may be optionally combined into several steps and operations, or extended to additional steps and operations.

The invention may sometimes describe different components contained within or associated with other different components. These described architectures are examples only, and many other architectures can be implemented to achieve the same or similar functionality.

The terms used in this disclosure and in the accompanying examples (eg, body of the accompanying examples) are generally intended as "open" terms (eg, the term "including" should be interpreted as "including but not limited to", the term "Has" should be interpreted as "having at least", the term "includes" should be interpreted as "including but not limited to", etc.), and furthermore, if a specific number of elements is introduced, this can be interpreted as meaning at least the recited number , as may be dictated by the context (eg, "two recitations" without other modifications of a bare recitation means at least two recitations or two or more recitations). As used herein, any transitional word and/or phrase denoting two or more alternative terms should be understood to include one of those terms, either of those terms, or both terms possibility. For example, the phrase "A or B" should be understood to include the possibilities of "A" or "B" or "A and B." Similarly, the phrase "A and/or B" should be understood to include the possibilities of "A" or "B" or "A and B".

Unless otherwise specified herein or clearly contradicted by context, the terms "a/an" and "the" and similar references are used to describe the context of the invention, especially in the context of the following examples It should be construed to cover both the singular and the plural. The use of any and all examples, or representative language (eg, "such as" or "such as") provided herein, is intended merely to better illuminate the invention and does not pose a limitation on the scope of any embodiment. No language in the specification herein should be construed as indicating any non-specified element as essential to the practice of the invention.

Groupings of alternative elements or embodiments disclosed herein should not be construed as limitations. Each group member may be referred to and embodied individually or in any combination with other members of the group or other elements found herein. It is contemplated that one or more members of a group may be included in or deleted from the group for reasons of convenience and/or patentability. When any such inclusion or deletion occurs, the specification is deemed to contain the group as modified, thus satisfying the written description for all Markush groups in the accompanying examples.

Certain embodiments are described herein, including the best mode known to the inventors for carrying out the invention. Of course, variations of those described embodiments will become apparent to those of ordinary skill upon reading the foregoing description. The inventors expect skilled artisans to employ such modifications as appropriate, and the inventors intend for the invention to be practiced unless specifically described herein. Accordingly, these examples are pre-licensed by applicable law. Moreover, unless otherwise indicated herein or otherwise clearly contradicted by context, any combination of the above-described elements in all possible variations thereof is contemplated. In conclusion, it should be understood that the embodiments disclosed herein illustrate the principles of such embodiments. Thus, by way of example, and not limitation, alternative embodiments may be utilized in light of the teachings herein. Accordingly, the embodiments are not limited to what is precisely shown and described herein.

EXAMPLES Example 1. A photoluminescent complex comprising: a blue light absorbing donor chromophore, wherein the donor chromophore comprises a naphthyl imide derivative; a linker complex; and a ring-locked boron- Dipyrromethane (BODIPY) moiety; wherein the linker complex covalently links the donor chromophore with the naphthyl imide derivative and the ring-locked BODIPY moiety, wherein the naphthyl imide derivative absorbs Excite blue light energy at a first wavelength and transfer energy to the ring-locked BODIPY moiety, wherein the ring-locked BODIPY moiety absorbs energy from the naphthylimide derivative and emits light energy at a second higher wavelength, and wherein The photoluminescent composite has an emission quantum yield greater than 80%.

Embodiment 2. The photoluminescent complex as in embodiment 1, wherein the naphthyl imide derivative of the donor chromophore has the following general formula: , wherein Y is selected from oxygen (O) or sulfur (S); wherein R ₇ and R ₈ are independently selected from hydrogen (H), substituted or unsubstituted aryl, or -CF ₃ ; and wherein R ₉ is independently is selected from hydrogen (H), substituted or unsubstituted aryl, C ₁ -C ₅ alkyl, or there is no substitution for R ₉ .

Embodiment 3. The photoluminescent complex as in embodiment 1, wherein the ring-locked BODIPY moiety has the general formula: , wherein R ₁ and R ₂ are independently selected from H or C ₁ -C ₃ alkyl; wherein R ₃ and R ₄ are independently selected from H, F, Br, -CF ₃ or a bond connected to LZ; wherein R ₅ and R ₆ is independently selected from H, C ₁ -C ₃ alkyl, halide or C ₁ -C ₃ alkoxy; and wherein X is independently selected from C ₁ -C ₃ alkyl, -CH ₂ CH ₂ - , -CH ₂ CH ₂ CH ₂ - or spirocycloalkyl.

Example 4. As in the photoluminescent complex of Example 3, wherein L is a linker complex, which can be a substituted ester, an unsubstituted ester, a substituted ether or an unsubstituted ether.

Example 5. The photoluminescent complex as in Example 3, wherein Z is a donor chromophore comprising a naphthylimide derivative.

Embodiment 6. The photoluminescent complex as in embodiment 1 or 4, wherein the linker complex is an unsubstituted ester; wherein the unsubstituted ester includes one of the following structures:

Embodiment 7. The photoluminescent complex as in embodiment 1 or 4, wherein the linker complex is a substituted ester; wherein the substituted ester comprises one of the following structures: , or .

Embodiment 8. The photoluminescent complex as in embodiment 1 or 4, wherein the linker complex is an unsubstituted and/or substituted ether; wherein the unsubstituted and/or substituted ether includes the following structure one of:

Embodiment 9. The photoluminescent compound according to claim 1, 2, 3, 4, 5, 6, 7 or 8, wherein the photoluminescent compound comprises one of the following structures: , or any combination thereof.

Example 10. A color conversion film comprising: Transparent substrate layer; a color conversion layer, wherein the color conversion layer comprises a resin matrix; and At least one photoluminescent compound dispersed in the resin matrix, wherein the at least one photoluminescent compound comprises the photoluminescent compound as in embodiment 1, 2, 3, 4, 5, 6, 7, 8 or 9 Complex.

Example 11. As in the color conversion film of Embodiment 10, it further comprises a singlet oxygen quencher.

Example 12. As in the color conversion film of Example 10, it further comprises a free radical scavenger.

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

Example 14. The color conversion film of Example 10, wherein the film absorbs light within a wavelength range of about 400 nm to about 480 nm and emits light within a wavelength range of about 590 nm to about 650 nm.

Example 15. A method for preparing a color conversion film as in embodiment 10, 11, 12, 13 or 14, the method comprising: Dissolving the photoluminescent composite and binder resin as in Example 1, 2, 3, 4, 5, 6, 7, 8 or 9 in a solvent; and The mixture is applied to one of the opposing surfaces of the transparent substrate.

Example 16. A backlight unit comprising the color conversion film of Embodiment 10, 11, 12, 13 or 14.

Example 17. A display device comprising the backlight unit of Embodiment 16.

EXAMPLES Embodiments of the photoluminescent composites described herein have been found to have improved performance, for example, compared to other forms of dyes used in color conversion films. These benefits are further demonstrated by the following examples, which are intended to illustrate the invention but are not intended to limit the scope or underlying principles in any way.

The following examples are synthetic procedures for many embodiments of naphthyl imide derivatives (ie, blue light absorbing intermediates) as described herein:

Example 1 (Ex-1) : Ex-1.1 : A mixture of 2-nitrophenol (6.6 g, 48 mmol), KOH powder (2.4 g, 43 mmol) was mixed and stirred under vacuum for 30 minutes, then copper powder (0.4 g) was added, followed by 100 mL Anhydrous DMF. The mixture was stirred for 5 minutes, then 4-chlorophthalic anhydride (5.1 g, 22 mmol) was added. The whole was degassed and then heated at 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 allowed to stand for 2 hours. The precipitate was collected by filtration, then dried under vacuum overnight to give a yellow-brown solid (4.6 g). It was further purified by stirring in refluxing acetic acid (50 mL) for 1 hour, then cooled to room temperature. Filtration and air drying afforded a yellow solid (3.0 g, 41% yield). Confirmed by _LCMS (APCI): Calcd. for _C18H10NO6 (M+H): 336.0; found: ₃₃₆ . ¹ H NMR (400 MHz, chloroform- d ) δ 8.80 (dd, J = 8.5, 1.2 Hz, 1H), 8.72 (dd, J = 7.3, 1.2 Hz, 1H), 8.50 (d, J = 8.2 Hz, 1H ), 8.19 (dd, J = 8.2, 1.7 Hz, 1H), 7.90 (dd, J = 8.5, 7.3 Hz, 1H), 7.79 (td, J = 7.9, 1.7 Hz, 1H), 7.54 (td, J = 8.0, 1.3 Hz, 1H), 7.39 (dd, J = 8.3, 1.2 Hz, 1H), 6.89 (d, J = 8.2 Hz, 1H).

Ex-1.2 : 4-(2-nitrophenoxy)-1,8-naphthoic anhydride (2.0 g, 6 mmol) and iron powder (<10 μm, 0.91 g, 16 mmol) of the mixture 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 and dried thoroughly in air, then placed under vacuum to give a yellow solid (1.65 g, 90% yield). Confirmed _by LCMS (APCI): Calcd. for _C18H12NO4 (M+H): 306.1 _; found: 306.

Ex-1.3 : Compound 4-(2-aminophenoxy)-1,8-naphthoic 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 a solution of sodium nitrite in 12 mL of water (3.29 g, 46 mmol) dropwise at 0 °C. The whole was stirred at 0 °C for one hour, then transferred to an addition funnel, and dropped into refluxing copper sulfate solution (5.08 g, 20 mmol, in 50 mL of water) over a period of 1 hour. After cooling to room temperature, the precipitate was collected by filtration, washed with water and acetone, then dried in air and then in vacuo to give a yellow solid (0.92 g, 65% yield). Confirmed by LCMS ( _APCI ): Calcd. for _C18H8O4 (M-): 288.0; found: ₂₈₈ . ¹ H NMR (400 MHz, chloroform- d ) δ 8.61 (dd, J = 17.1, 8.1 Hz, 2H), 8.09 (d, J = 8.0 Hz, 1H), 7.97 (d, J = 7.9 Hz, 1H), 7.59 (t, J = 7.7 Hz, 1H), 7.40 (t, J = 8.1 Hz, 2H), 7.33 (d, J = 8.4 Hz, 1H).

Ex-1 : 1H,3H-iso[6,5,4-mna][6,5,4-mna] in 5 mL DMF - A mixture of 1,3-dione (100 mg, 0.347 mmol), 2-(4-aminophenyl)acetic acid (135 mg, 0.9 mmol) was heated in a microwave reactor at 165°C for 2 hours. 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 and washed with acetone, dried in air to give a yellow solid (88 mg, 61% Yield). Confirmed _by LCMS (APCI): Calcd. for _C26H15NO5 (M-): 421.1; found: 421 _. ¹ H NMR (400 MHz, DMSO- d ₆ ) δ 8.27 (d, J = 45.1 Hz, 4H), 7.67 - 7.00 (m, 8H), 3.58 (s, 2H).

Example 2 (Ex-2): Ex-2 : 1H,3H-iso[6,5,4-mna][6,5,4-mna]𠮿 contained in 5 mL of DMF - A mixture of 1,3-dione (100 mg, 0.347 mmol), 4-(4-aminophenyl)butanoic acid (125 mg, 0.7 mmol) was heated in a microwave reactor at 165°C for 2.5 hours. 15 mL of acetone was added to the mixture, and the resulting precipitate was collected by filtration and dried in air, then in a vacuum oven at 100 °C for 1 hour to give a yellow solid (120 mg, 77% yield). Confirmed _by LCMS (APCI): Calcd. for _C28H19NO5 (M-): 449.1; found: ₄₄₉ . ¹ H NMR (400 MHz, DMSO- d ₆ ) δ 8.38 (d, J = 41.6 Hz, 4H), 7.81 - 6.97 (m, 8H), 2.69 - 2.64 (m, 2H), 2.26 (t, J = 7.2 Hz, 2H), 1.87 (p, J = 7.2 Hz, 2H).

Example 3 (Ex-3) : Ex -3.1 : To a mixture of compound Ex-1.3 (290 mg, 1.0 mmol) in n-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 yellow solid as the desired product. The filtrate was loaded onto silica gel and purified by flash chromatography using the eluent of hexane/dichloromethane (50% à 100% dichloromethane). The desired fractions were collected and the solvent was removed to give 110 mg of a yellow solid. 400 mg of total product were obtained, yield 89.7%. LCMS (APCI-): Calcd. _{for Ci8H6Br2O4 : 443.9} ; found: 444. ¹ H NMR (400 MHz, d ₂ -TCE) δ 9.40 (dd, J = 8.5, 1.5 Hz, 1H), 8.71 (s, 1H), 8.67 (s, 1H), 7.60 (ddd, J = 8.4, 7.1 , 1.5 Hz, 1H), 7.48 (dd, J = 8.3, 1.4 Hz, 1H), 7.38 (ddd, J = 8.5, 7.1, 1.4 Hz, 1H).

Ex-3.2 : Compound Ex -3.1 (190 mg, 0.426 mmol), 4-(4-aminophenyl)butyl in anhydrous N,N-dimethylformamide (DMF) (4 mL) A mixture of acid (180 mg, 0.64 mmol), 4-(N,N-dimethylamino)-pyridine (4 mg) was heated at 165°C for 2.5 hours. After cooling the mixture to room temperature and standing 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-): Calcd. _{for C28H17Br2NO5} : _604.95 ; found: 605. ¹ H NMR (400 MHz, DMSO- d ₆ ) δ 9.42 (dd, J = 8.6, 1.5 Hz, 1H), 8.57 (d, J = 4.6 Hz, 2H), 7.83 - 7.68 (m, 1H), 7.63 - 7.44 (m, 2H), 7.34 (d, J = 8.3 Hz, 2H), 7.31 - 7.16 (m, 2H), 2.67 (dd, J = 4.8, 2.8 Hz, 2H), 2.28 (t, J = 7.4 Hz , 2H), 1.95 - 1.80 (m, 2H).

Ex-3 : Compound Ex -3.2 (100 mg, 0.165 mmol), (3,5-bis(trifluoromethyl)phenyl)boronic acid (170 mg) contained in THF/water (5 mL/0.5 mL) , 0.66 mmol), Pd(dppf)Cl2 (20 mg, 0.027 mmol) and potassium carbonate (138 mg, 1 mmol) was degassed and then heated at 80°C for 2 hours. After cooling to room temperature, the precipitate was collected by filtration, washed with acetone, and then dried in a vacuum oven at 90° C. for 2 hours. A yellow solid was obtained (142 mg, 94% yield). LCMS ( _APCI- ): Calcd. _{for C44H23F12NO5 :} 873.14; found: 873. ¹ H NMR (400 MHz, d ₂ -TCE) δ 8.65 (s, 1H), 8.40 (s, 1H), 8.17 (s, 2H), 7.96 (d, J = 19.3 Hz, 4H), 7.38 (d, J = 8.4 Hz, 1H), 7.33 (d, J = 8.0 Hz, 2H), 7.18 (d, J = 8.0 Hz, 3H), 6.90 (d, J = 6.3 Hz, 2H), 2.72 (t, J = 7.6 Hz, 2H), 2.38 (t, J = 7.4 Hz, 2H), 2.03 - 1.93 (m, 2H).

Example 4 (Ex-4) : Ex-4.1 : A mixture of 4-bromo-1,8-naphthoic anhydride (2.77 g, 10 mmol), 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, then heated at 180 °C overnight under an atmosphere of argon. After the mixture was cooled down 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 in vacuo to afford 4.6 g of crude product. The crude product was dispersed in 30 mL of acetone and stirred overnight at room temperature to dissolve impurities. Filtration and drying in vacuo afforded a tan solid as the desired product (3.3 g, 80% yield). LCMS ₍ APCI+): Calcd. for _Ci8H9BrNO6 (M+H) = 413.95; found: ₄₁₄ . ¹ H NMR (400 MHz, TCE-d ₂ ) δ 8.70 (dd, J = 8.4, 1.2 Hz, 1H), 8.63 (dd, J = 7.3, 1.2 Hz, 1H), 8.41 (d, J = 8.3 Hz, 1H), 8.24 (d, J = 2.4 Hz, 1H), 7.89 - 7.79 (m, 2H), 7.20 (d, J = 8.7 Hz, 1H), 6.82 (d, J = 8.3 Hz, 1H).

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 while stirring. The resulting mixture was filtered and washed with water, dried in air and vacuum to give a solid (1.35 g, 82% yield). LCMS (APCI-): Calcd. for _C18H10BrNO4 = _382.98 ; found: ₃₈₃ . ¹ H NMR (400 MHz, DMSO- d ₆ ) δ 9.01 - 8.26 (m, 3H), 7.96 (s, 1H), 6.93 (dd, J = 85.2, 36.5 Hz, 4H), 5.54 (s, 2H).

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 a solution of sodium nitrite (3.57 g, 52 mmol) in 15 mL of water at 0 °C dropwise. The whole was stirred at 0 °C for one 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 a period of 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, air and then vacuum drying afforded a tan solid (1.76 g, 70% yield). LCMS ₍ APCI+): Calcd for _Ci8H8BrO4 (M+H) = _366.95 ; found: 367. ¹ H NMR (400 MHz, d ₂ -TCE) δ 8.51 (dd, J = 12.3, 8.1 Hz, 2H), 8.12 (d, J = 2.3 Hz, 1H), 7.86 (d, J = 7.9 Hz, 1H) , 7.60 (dd, J = 8.8, 2.3 Hz, 1H), 7.28 (d, J = 8.3 Hz, 1H), 7.23 (d, J = 8.8 Hz, 1H).

Ex-4.4 : 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) was heated in a microwave reactor at 165°C for 2.5 hours. The resulting solution was dropped into 50 mL of acetone while stirring. A precipitate formed and was filtered and dried in a vacuum oven at 60°C overnight to give the desired product (0.49 g, 62% yield) as a tan solid. LCMS (APCI-): _Calcd . for _C28H18BrNO5 = _527.04 ; found: 527. ¹ H NMR (400 MHz, DMSO- d ₆ ) δ 8.54 (d, J = 2.3 Hz, 1H), 8.41 (dd, J = 9.9, 8.0 Hz, 2H), 8.33 (d, J = 7.9 Hz, 1H) , 7.71 (dd, J = 8.8, 2.3 Hz, 1H), 7.39 (dd, J = 8.6, 4.2 Hz, 2H), 7.25 (d, J = 8.0 Hz, 2H), 7.17 (d, J = 7.9 Hz, 2H), 2.63 - 2.55 (m, 2H), 2.27 - 2.15 (m, 2H), 1.87 - 1.73 (m, 2H).

Ex-4 : Compound Ex-4.4 (385 mg, 0.729 mmol), phenylboronic acid (178 mg, 1.45 mmol), Pd in a co-solvent of THF/DMF/water (20L/4 mL/2 mL) A mixture of (dppf) _Cl2 (36 mg, 0.05 mmol), potassium carbonate (276 mg, 2 mmol) was degassed and then heated at 80 °C overnight. The mixture was treated 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 x 2). The organic phase was collected and washed with brine (100 mL x 2), dried over sodium sulfate, then dry loaded onto silica gel and eluted by flash chromatography using DCM/EA (0% to 40% EA with 0.1% TFA) Reagent purification. The main desired fractions were collected and the solvent was removed under reduced pressure to give a yellow solid (250 mg, 65% yield). LCMS (APCI-): Calcd. for _C34H23NO5 = _525.16 ; found: 525 _. ¹ H NMR (400 MHz, TCE-d ₂ ) δ 8.55 (dd, J = 19.5, 8.1 Hz, 2H), 8.20 (d, J = 2.1 Hz, 1H), 8.01 (d, J = 8.1 Hz, 1H) , 7.72 (dd, J = 8.6, 2.1 Hz, 1H), 7.62 (d, J = 7.3 Hz, 2H), 7.51 - 7.28 (m, 7H), 7.17 (d, J = 8.2 Hz, 2H), 2.72 ( t, J = 7.7 Hz, 2H), 2.39 (t, J = 7.3 Hz, 2H), 1.99 (q, J = 7.2 Hz, 2H).

Example 5 (Ex-5) Ex-5 : Compound Ex-4.4 (385 mg, 0.729 mmol), 3,5-bis(trifluoromethyl)benzene in a co-solvent of THF/DMF/water (20L/4 mL/2 mL) A mixture of boronic acid (374 mg, 1.45 mmol), Pd(dppf)Cl ₂ (36 mg, 0.05 mmol), potassium carbonate (276 mg, 2 mmol) was degassed and then heated at 80°C overnight. The mixture was treated with 200 mL of ethyl acetate and 50 mL of 0.6N aqueous hydrochloric acid. The aqueous phase was extracted with ethyl acetate (100 mL x 2). The organic phase was collected and washed with brine (100 mL x 2), dried over sodium sulfate, then dry loaded onto silica gel and eluted by flash chromatography using DCM/EA (0% to 40% EA with 0.1% TFA) Reagent purification. The main desired fractions were collected and the solvent was removed under reduced pressure to give a yellow solid (340 mg, 70.5% yield). LCMS ₍ APCI-): Calcd. _{for C36H21F6NO5} = _661.13 ; found: 661. ¹ H NMR (400 MHz, d ₂ -TCE) δ 8.57 (dd, J = 19.2, 8.1 Hz, 2H), 8.18 (d, J = 2.2 Hz, 1H), 8.05 (d, J = 8.0 Hz, 1H) , 8.03 - 7.98 (m, 2H), 7.87 (s, 1H), 7.72 (dd, J = 8.6, 2.2 Hz, 1H), 7.48 (d, J = 8.6 Hz, 1H), 7.33 (d, J = 8.3 Hz, 3H), 7.21 - 7.12 (m, 2H), 2.72 (t, J = 7.6 Hz, 2H), 2.39 (t, J = 7.3 Hz, 2H), 2.04 - 1.97 (m, 2H).

Example 6 (Ex-6) Ex-6 : 1H,3H-sulfur 𠮿 contained in 10 mL DMF [2,1,9-def]iso-1,3-dione (458 mg, 1.5 mmol), 4-(4-aminophenyl)butanoic acid (537 mg, 3 mmol) and DMAP (14 mg, 0.11 mmol) was heated in a microwave reactor at 165°C for 2.5 hours. The resulting solution was dropped into 60 mL of acetone while stirring. An orange precipitate formed and was filtered and washed with ether, dried in air to give an orange solid (546 mg), which was further dried in a vacuum oven at 100 °C for 3 hours to give the desired product as an orange solid (500 mg, 71.7% yield). Confirmed by LCMS (APCI-): calcd for _{C28H19NO4S = 465.10} ; found: 465. ¹ H NMR (400 MHz, DMSO- d ₆ ) δ 8.55 (d, J = 8.4 Hz, 1H), 8.52 - 8.46 (m, 2H), 8.32 (d, J = 8.0 Hz, 1H), 7.78 (d, J = 8.0 Hz, 1H), 7.65 - 7.58 (m, 1H), 7.52 (tt, J = 7.2, 5.5 Hz, 2H), 7.37 - 7.30 (m, 2H), 7.30 - 7.23 (m, 2H), 2.69 (t, J = 7.4 Hz, 2H), 2.29 (t, J = 7.3 Hz, 2H), 1.88 (p, J = 7.5 Hz, 2H).

The following example is a synthetic procedure for a number of embodiments of pyrrole intermediates as described herein: Example 7 (Ex-7.3) : Ex-7.2 - General synthetic procedure for compound Ex-7.2 , (E)-6,7,8,9- tetrahydro -5H- benzo [7] annulene -5- one oxime: will be contained in EtOH/H ₂ A mixture of compound Ex-7.1 (10.0 g, 62.0 mmol), NH ₂ OH•HCl (6.50 g, 93.0 mmol) and NaOAc (12.7 g, 155.0 mmol) in O (45 mL/150 mL) was put into 500 mL with In a two-neck round bottom flask with a reflux condenser. The solution was heated up to 115°C to reflux and held at this temperature for 1 hour. TLC (50% EtOAc/hexanes) showed the reaction was complete. After cooling down to 0° C. and filtration, compound Ex-7.2 was obtained as an off-white solid and used in the next step without further purification, quantitative yield. MS (APCI): Calcd. for _C11H14NO ([M+H] ⁺ ) = 176 Found: ₁₇₆ . ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.98 (bs, 1H), 7.39 (dd, J = 7.6 Hz, 1.6 Hz, 1H), 7.30 (td, J = 7.6 Hz, 1.6 Hz, 1H), 7.23 ( td, J = 7.6 Hz, 1.6 Hz, 1H), 7.13 (d, J = 7.6 Hz, 1H), 2.74 (m, 4H), 1.78 (ddd, J = 13.2 Hz, 6.0 Hz, 6.0 Hz, 2H), 1.65 (ddd, J = 12.4 Hz, 6.0 Hz, 6.0 Hz, 2H).

Ex-7.3 - General Synthetic Procedure for Compound Ex-7.3 , 1,4,5,6- Tetrahydrobenzo [6,7] cyclohepta [1,2-b] pyrrole: In DMSO (50 mL) A solution of compound Ex-7.2 (8.8 g, 50.0 mmol) and KOH (10.1 g, 180.0 mmol) was put into a 250 mL two-neck round bottom flask with a reflux condenser. The solution was degassed at room temperature and heated up to 140°C. To this solution was added dropwise via syringe pump an additional solution of DCE (12.4 g, 125 mmol) in DMSO (50 mL) over 5.5 hours. After the addition of the DCE solution was complete, the reaction was cooled to room temperature, then poured into saturated _NH4Cl solution (500 mL). The desired product was extracted from the work-up solution using EtOAc (500 mL*3). The combined organic layers were dried over _{anhydrous Na2SO4} , concentrated in vacuo and purified by silica gel flash chromatography using DCM in hexane (0 to 30%) as eluent to give the compound as off-white solid Ex-7.3 , 4.6 g, 50% yield. MS (APCI): Calcd. for _C13H14N ([M+H] ⁺ ) = 184 Found: ₁₈₄ . ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.19 (bs, 1H), 7.34 (dd, J = 8.0 Hz, 1.6 Hz, 1H), 7.22 (td, J = 7.6 Hz, 1.6 Hz, 1H), 7.16 ( dd, J = 7.6 Hz, 1.6 Hz, 1H), 7.09 (td, J = 7.6 Hz, 1.6 Hz, 1H), 6.84 (t, J = 2.8 Hz, 1H), 6.16 (t, J = 2.8 Hz, 1H ), 2.90 (t, J = 6.8 Hz, 2H), 2.83 (m, 2H), 2.02 (m, 2H).

Example 8 (Ex-8.2) : Compound Ex-8.2 , the general synthesis procedure of 4,5- dihydro -1H- benzo [g] indole: NH ₂ OH·HCl (4.2 g, 60.0 mmol) and KOH in DMSO (50 mL) (3.4 g, 60.0 mmol) of the mixture was placed in a 500 mL two necked round bottom flask with a reflux condenser. The solution was stirred at room temperature for 30 minutes. Compound Ex-8.1 (7.3 g, 50.0 mmol) in DMSO (25 mL) was then added. The solution was heated up to 70°C and held at this temperature for 30 minutes. Then, another portion of KOH (8.4 g, 150.0 mmol) was added to the solution, and the solution was heated up to 140°C. To this solution was added dropwise via syringe pump an additional solution of DCE (9.9 g, 100.0 mmol) in DMSO (25 mL) over 4 hours. After the addition of the DCE solution was complete, the reaction was cooled to room temperature, then poured into saturated _NH4Cl solution (200 mL). The desired product was extracted from the work-up solution using EtOAc (200 mL*3). The combined organic layers were dried over _{anhydrous Na2SO4} , concentrated in vacuo and purified by silica gel flash chromatography using DCM in hexane (0 to 30%) as eluent to give the compound as off-white solid Ex-8.2 , 3.7 g, 43% yield. MS (APCI): Calcd. for _C12H12N ([M+H] ⁺ ) = 170 Found: ₁₇₀ . ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.28 (bs, 1H), 7.22 (ddd, J = 17.6 Hz, 10.4 Hz, 10.4 Hz, 2H), 7.16 (t, J = 7.2 Hz, 1H), 7.08 ( td, J = 7.2, 1.6 Hz, 1H), 6.76 (m, 1H), 6.15 (m, 1H), 2.96 (t, J = 7.2 Hz, 2H), 2.78 (t, J = 7.2 Hz, 2H).

Example 9 - Synthesis of Photoluminescent Complex (PLC) : The following example is a synthetic procedure for a number of embodiments of RL-naphthylimide-BODIPY as described herein: Synthesis of PLC-1 : General procedure for compound PLC-1.3 : A 100 mL 2-neck round bottom flask was equipped with an air condenser and a stirring bar. To this flask was added compound 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) followed by addition of anhydrous dichloroethane (55 ml). The reaction mixture was sparged with Ar for 30 min, then TFA (4 drops) was added. The reaction solution was stirred overnight at room temperature. After cooling the reaction down to 0 °C in an ice-water bath, p-chloranil (731.8 mg, 2.98 mmol) was added. The reaction was maintained at 0°C for 30 minutes. Then BF ₃ •OEt ₂ (3.0 mL, 24.1 mmol) and Et ₃ N (1.9 mL, 13.3 mmol) were added at 0°C. The reaction mixture was heated up to 50 °C for 3 hours. The reaction mixture was loaded on silica gel and purified by flash chromatography using DCM in hexane (0 to 80% to 90%) as eluent to give pure BODIPY PLC-1.3 as a brown-golden solid, 476.0 mg, 36% yield. MS ( _APCI ) _{: Calcd} . for _{C33H24BCl2F2N2O} ([MH] ^- ) = ₅₈₄ Found: 584. ¹ H NMR (400 MHz, CDCl ₃ ) 8.09 (dd, J = 4.0 Hz, 2.0 Hz, 2H), 7.32 (dddd, J = 13.2 Hz, 7.2 Hz, 7.2 Hz, 2.0 Hz, 4H), 7.22 (dd, J = 6.4 Hz, 2.0 Hz, 2H), 6.99 (s, 2H), 6.43 (s, 2H), 5.77 (bs, 1H), 2.63 (dd, J = 6.8 Hz, 6.8 Hz, 4H), 2.32 (bs , 4H), 2.03 (ddd, J = 14.0 Hz, 6.8 Hz, 6.8 Hz, 4H).

General procedure for compound PLC-1 : A 10 mL vial was fitted with a stir bar. Add compound 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) in this vial, Then dry DCM (1.5 ml) was added. The reaction mixture was heated up to 40 °C overnight. After cooling the reaction down to room temperature, the reaction mixture was loaded on silica gel and purified by flash chromatography using EtOAc (0 to 5%) with DCM as eluent to give pure RL-naphthalene as a dark purple solid Amide-BODIPY PLC-1 . The solid was further triturated with MeOH (10 ml) to give RL-naphthylimide-BODIPY PLC-1 , 21.0 mg, 48% yield. MS _{( APCI} ) _{: Calcd .} for _{C61H41Cl2F2N3O5} ([MH] ^- ) = 1015 Found: 1015. ¹ H NMR (400 MHz, CDCl ₃ ) 8.66 (dd, J = 18.4 Hz, 7.6 Hz, 2H), 8.10 (m, 3H), 7.99 (d, J =8.0 Hz, 1H), 7.56 (ddd, J = 8.0 Hz, 8.0 Hz, 1.6 Hz, 1H), 7.36 (m, 13H), 7.22 (dd, J = 6.8 Hz, 2.0 Hz, 2H), 6.45 (s, 2H) 2.88 (t, J = 7.6 Hz, 2H ), 2.72 (t, J = 7.2 Hz, 2H), 2.63 (m, 4H), 2.20 (m, 6H), 2.04 (ddd, J = 6.8 Hz, 6.8 Hz, 6.8 Hz, 4H).

Synthesis of PLC-2 : General procedure for compound PLC-2 : 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) was stirred overnight at room temperature. The resulting mixture was then loaded onto silica gel and purified by flash chromatography using the eluent of DCM/ethyl acetate (0%→5% ethyl acetate). The main red fractions were collected and concentrated under reduced pressure to about 1 mL, then 10 mL of methanol was added. The resulting precipitate was filtered and air dried to give a dark red solid (41 mg, 70.8% yield). _LCMS (APCI-) _: Calcd _{. for C67H46BCl2F2N3O5} (M-) = _1091.29 ; found: 1091. ¹ H NMR (400 MHz, d ₂ -TCE) δ 8.56 (dd, J = 19.3, 8.1 Hz, 2H), 8.21 (d, J = 2.2 Hz, 1H), 8.02 (d, J = 8.1 Hz, 1H) , 7.97 (t, J = 4.7 Hz, 2H), 7.73 (dd, J = 8.6, 2.1 Hz, 1H), 7.63 (dd, J = 7.2, 1.7 Hz, 2H), 7.50 - 7.41 (m, 3H), 7.38 (dd, J = 8.0, 2.2 Hz, 3H), 7.34 - 7.25 (m, 7H), 7.25 - 7.18 (m, 4H), 6.40 (s, 2H), 2.82 (t, J = 7.5 Hz, 2H) , 2.67 (t, J = 7.4 Hz, 2H), 2.60 - 2.49 (m, 4H), 2.24 (s, 4H), 2.18 - 2.07 (m, 2H), 2.03 - 1.90 (m, 4H).

Synthesis of PLC-3 : General procedure for Compound PLC-3 : 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), a mixture of DMAP/TsOH salt (29 mg, 0.1 mmol) was stirred at room temperature for 40 hours. The resulting mixture was loaded onto silica gel and purified by flash chromatography using the eluent of hexane/dichloromethane (50%→100% dichloromethane). Collect the desired fractions. After removing the solvent and washing with methanol, a dark red solid (45 mg, 65% yield) was obtained after filtration and air drying. _LCMS ( _APCI- ): _Calcd . _{for C77H46BCl2F14N3O5} (M-) = _1439.27 ; found: 1439. ¹ H NMR (400 MHz, d ₂ -TCE) δ 8.66 (s, 1H), 8.41 (s, 1H), 8.18 (d, J = 1.5 Hz, 2H), 7.96 (d, J = 18.4 Hz, 6H) , 7.39 (dd, J = 8.3, 2.4 Hz, 3H), 7.34 - 7.12 (m, 11H), 6.98 - 6.85 (m, 2H), 6.39 (s, 2H), 2.82 (t, J = 7.6 Hz, 2H ), 2.66 (t, J = 7.4 Hz, 2H), 2.54 (d, J = 6.1 Hz, 4H), 2.24 (m, 4H), 2.15 - 2.06 (m, 2H), 1.96 (m, 4H).

Synthesis of PLC-4 : General procedure for compound PLC-4.3 : A 100 mL 2-neck round bottom flask was equipped with an air condenser and a stirring bar. To this flask was added compound 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), followed by the addition of anhydrous dichloroethane (15 ml). The reaction mixture was sparged with Ar for 30 min, then TFA (3 drops) was added. The reaction solution was heated up to 40°C and stirred overnight at 40°C. After cooling the reaction down to 0 °C in an ice-water bath, p-chloranil (200.0 mg, 0.8 mmol) was added. The reaction was maintained at 0°C for 30 minutes. Then BF ₃ •OEt ₂ (0.8 mL, 6.5 mmol) and Et ₃ N (0.5 mL, 3.6 mmol) were added at 0°C. The reaction mixture was heated up to 50 °C for 2 hours. The reaction mixture was loaded on silica gel and purified by flash chromatography using DCM in hexane (0 to 80% to 90%) as eluent to give pure BODIPY PLC-4.3 as a dark purple gold solid, 242.2 mg, 78 %Yield. MS ₍ APCI) _: Calcd. for _C33H28BF2N2O ([M+H] ⁺ ) = 517 Found _: 517. ¹ H NMR (400 MHz, CDCl ₃ ) 8.80 (d, J = 8.0 Hz, 2H), 7.44 (td, J = 7.2 Hz, 1.6 Hz, 2H), 7.31 (td, J = 7.6 Hz, 1.2 Hz, 2H ), 7.25 (m, 2H), 6.63 (s, 2H), 6.33 (s, 2H), 4.82 (s, 1H), 2.91 (t, J = 6.4 Hz, 4H), 2.65 (t, J = 6.4 Hz , 4H), 2.18 (s, 6H).

General procedure for compound PLC-4 : A 10 mL vial was fitted with a stir bar. Add compound 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) in this vial, Then dry DCM (1.5 ml) was added. The reaction mixture was heated up to 40 °C overnight. After cooling the reaction down to room temperature, the reaction mixture was loaded on silica gel and purified by flash chromatography using EtOAc (0 to 5%) with DCM as eluent to give pure RL-naphthoyl as a blue-green solid Imine-BODIPY PLC-4 . The solid was further triturated with MeOH (10 ml) to give RL-naphthylimide-BODIPY PLC-4 , 20.1 mg, 44% yield. MS ₍ APCI) _: Calcd. for _{C6iH43BF2N3O5} ([MH] ^- ) = ₉₄₇ Found: ₉₄₇ . ¹ H NMR (400 MHz, CDCl ₃ ) 8.80 (d, J = 8.4 Hz, 2H), 8.66 (dd, J = 18.4 Hz, 8.0 Hz, 2H), 8.11 (dd, J = 8.0 Hz, 1.6 Hz, 1H ), 7.99 (d, J = 8.0 Hz, 1H), 7.56 (ddd, J = 8.0 Hz, 8.0 Hz, 1.6 Hz, 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).

Synthesis of PLC-5 : General procedure for compound PLC-5.3 : A 100 mL 2-neck round bottom flask was equipped with an air condenser and a stirring bar. To this flask was added 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), followed by addition of anhydrous dichloroethane (15 ml). The reaction mixture was sparged with Ar for 30 min, then TFA (3 drops) was added. The reaction solution was stirred overnight at room temperature. After cooling the reaction down to 0 °C in an ice-water bath, p-chloranil (200.0 mg, 0.8 mmol) was added. The reaction was maintained at 0°C for 30 minutes. Then BF ₃ •OEt ₂ (0.8 mL, 6.5 mmol) and Et ₃ N (0.5 mL, 3.6 mmol) were added at 0°C. The reaction mixture was heated up to 50 °C for 2 hours. The reaction mixture was loaded on silica gel and purified by flash chromatography using DCM in hexane (0 to 80% to 90%) as eluent to give pure BODIPY PLC-5.3 as a dark purple gold solid, 200.3 mg, 57 %Yield. MS ( _APCI ): Calcd. _{for C31H20BCl2F2N2O} ([MH] ⁻ ) = ₅₅₆ Found _: 556. ¹ H NMR (400 MHz, CDCl ₃ ) 8.80 (d, J = 8.0 Hz, 2H), 7.44 (td, J = 7.6 Hz, 1.6 Hz, 2H), 7.32 (td, J = 7.6 Hz, 1.2 Hz, 2H ), 7.25 (m, 2H), 6.99 (s, 2H), 6.35 (s, 2H), 5.68 (bs, 1H), 2.93 (t, J = 7.6 Hz, 4H), 2.68 (t, J = 7.6 Hz , 4H).

General procedure for compound PLC-5 : A 10 mL vial was fitted with a stir bar. Add compound 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) in this vial, Then dry DCM (1.5 ml) was added. The reaction mixture was heated up to 40 °C overnight. After cooling the reaction down to room temperature, the reaction mixture was loaded on silica gel and purified by flash chromatography using EtOAc in DCM (0 to 5%) as eluent to give pure RL-naphthylidene as a green solid Amine - BODIPY PLC-5 . The solid was further triturated with MeOH (10 ml) to give RL-naphthylimide-BODIPY PLC-5 , 16.0 mg, 36% yield. MS _{( APCI} ) _: Calcd. _{for C59H37BCl2F2N3O5} ([MH] ^- ) = 986 Found: ₉₈₆ . ¹ H NMR (400 MHz, CDCl ₃ ) 8.80 (d, J = 8.4 Hz, 2H), 8.66 (dd, J = 18.0 Hz, 8.0 Hz, 2H), 8.11 (dd, J = 8.0 Hz, 1.6 Hz, 1H ), 7.99 (d, J = 8.0 Hz, 1H), 7.56 (ddd, J = 8.0 Hz, 8.0 Hz, 1.6 Hz, 1H), 7.34 (m, 15H), 6.37 (s, 2H), 2.90 (m, 6H), 2.70 (dd, J = 14.8 Hz, 7.6 Hz, 6H), 2.24 (ddd, J = 7.6 Hz, 7.6 Hz, 7.6 Hz, 2H).

Synthesis of PLC-6 : General procedure of PLC-6.3 : Install an air condenser and a stirring bar in a 100 mL 2-neck round bottom flask. Add compound 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-Dimethoxybenzaldehyde PLC-6.2 (109.3 mg, 0.6 mmol) followed by addition of anhydrous dichloroethane (15 ml). The reaction mixture was sparged with Ar for 30 min, then TFA (3 drops) was added. The reaction solution was heated up to 40°C and stirred overnight at 40°C. After cooling the reaction down to 0 °C in an ice-water bath, p-chloranil (200.0 mg, 0.8 mmol) was added. The reaction was maintained at 0°C for 30 minutes. Then BF ₃ •OEt ₂ (0.8 mL, 6.5 mmol) and Et ₃ N (0.5 mL, 3.6 mmol) were added at 0°C. The reaction mixture was heated up to 50 °C for 2 hours. The reaction mixture was loaded on silica gel and purified by flash chromatography using DCM in hexane (0 to 80% to 90%) as eluent to give pure BODIPY PLC-6.3 as a dark purple solid, 28.0 mg, 8% yield Rate. MS (APCI) _: Calcd. for _{C35H30BF2N2O3} ([MH]-) = 576 Found _{: 576 .} ¹ H NMR (400 MHz, CDCl3) 8.10 (d, J = 7.6 Hz, 2H), 7.29 (dddd, J = 17.2 Hz, 7.2 Hz, 7.2 Hz, 4H), 7.21 (dd, J = 7.2 Hz, 2H) , 6.48 (s, 2H), 6.19 (s, 2H), 3.72 (s, 6H), 2.62 (dd, J = 6.8 Hz, 6.8 Hz, 4H), 2.29 (bs, 4H), 2.02 (ddd, J = 14.0 Hz, 7.2 Hz, 7.2 Hz, 4H).

General procedure for PLC-6 : Install a 10 mL vial with a stir bar. Add compound 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) in this vial, Then dry DCM (1.5 ml) was added. The reaction mixture was heated up to 40 °C overnight. After cooling the reaction down to room temperature, the reaction mixture was loaded on silica gel and purified by flash chromatography using EtOAc in DCM (0 to 5%) as eluent to give pure RL-naphthoyl as a dark reddish-purple solid Imine-BODIPY PLC-6 . The solid was further triturated with MeOH (10 ml) to give RL-naphthylimide-BODIPY PLC-6 , 4.0 mg, 8% yield. MS ₍ APCI) _{: Calcd} . for _{C63H47BF2N3O7} ([MH] ^- ) = 1007 Found _: 1007. ¹ H NMR (400 MHz, CDCl ₃ ) 8.66 (dd, J = 18.4 Hz, 8.0 Hz, 2H), 8.11 (dd, J = 8.0 Hz, 1.6 Hz, 3H), 7.99 (d, J = 8.0 Hz, 1H ), 7.56 (ddd, J = 8.0 Hz, 8.0 Hz, 1.6 Hz, 1H), 7.41 (m, 4H), 7.32 (m, 7H), 7.21 (dd, J = 7.2 Hz, 1.6 Hz, 2H), 6.50 (s, 2H), 6.49 (s, 2H), 3.77 (s, 6H), 2.89 (t, J = 7.2 Hz, 2H), 2.72 (t, J = 7.2 Hz, 2H), 2.62 (m, 4H) , 2.30 (bs, 2H), 2.21 (ddd, J = 7.6 Hz, 7.6 Hz, 7.6 Hz, 4H), 2.02 (ddd, J = 6.8 Hz, 6.8 Hz, 6.8 Hz, 4H).

Synthesis of PLC-7 : General procedure of PLC-7.3 : Install an air condenser and a stirring bar in a 100 mL 2-neck round bottom flask. To this flask was added compound 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), followed by anhydrous dichloroethane (15 ml). The reaction mixture was sparged with Ar for 30 min, then TFA (3 drops) was added. The reaction solution was heated up to 40°C and stirred overnight at 40°C. After cooling the reaction down to 0 °C in an ice-water bath, p-chloranil (200.0 mg, 0.8 mmol) was added. The reaction was maintained at 0°C for 30 minutes. Then BF ₃ •OEt ₂ (0.8 mL, 6.5 mmol) and Et ₃ N (0.5 mL, 3.6 mmol) were added at 0°C. The reaction mixture was heated up to 50 °C for 2 hours. The reaction mixture was loaded on silica gel and purified by flash chromatography using DCM in hexane (0 to 80% to 90%) as eluent to give pure BODIPY PLC-7.3 as a brown-golden solid, 78.4 mg, 24% Yield. MS (APCI): _{Calcd .} for _{C33H28BF2N2O3} ([M+H] ⁺ ) = ₅₄₉ Found _: 549. ¹ H NMR (400 MHz, CDCl ₃ ) 8.80 (d, J = 8.0 Hz, 2H), 7.43 (t, J = 8.0 Hz, 2H), 7.29 (m, 2H), 7.23 (d, J = 7.2 Hz, 2H), 6.41 (s, 2H), 6.17 (s, 2H), 5.05 (bs, 1H), 3.69 (s, 6H), 2.90 (t, J = 6.8 Hz, 4H), 2.65 (t, J = 6.8 Hz, 4H).

General procedure for PLC-7 : Install a 10 mL vial with a stir bar. Add compound 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 (24.7 mg, 0.091 mmol) in this vial, Then dry DCM (1.5 ml) was added. The reaction mixture was heated up to 40 °C overnight. After cooling the reaction down to room temperature, the reaction mixture was loaded on silica gel and purified by flash chromatography using EtOAc in DCM (0 to 5%) as eluent to give pure RL-naphthylamide as a dark green solid imine-BODIPY PLC-7 . The solid was further triturated with MeOH (10 ml) to give RL-naphthylimide-BODIPY PLC-7 , 23.0 mg, 51% yield. MS _{(APCI): Calcd. for C6iH43BF2N3O7 ( [ MH} ] ^- ) = ₉₇₉ Found: 979. ¹ H NMR (400 MHz, CDCl ₃ ) 8.81 (d, J = 8.0 Hz, 2H), 8.67 (dd, J = 18.4 Hz, 7.6 Hz, 2H), 8.11 (dd, J = 8.0 Hz, 1.6 Hz, 1H ), 8.00 (d, J = 8.0 Hz, 1H), 7.56 (ddd, J = 8.0 Hz, 8.0 Hz, 1.6 Hz, 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 = 14.0 Hz, 6.4 Hz, 6H), 2.68 (m, 6H), 2.24 (ddd, J = 7.6 Hz, 7.6 Hz , 7.6 Hz, 2H).

Synthesis of PLC-8 : General procedure of PLC-8.3 : Install a 100 mL 2-neck round bottom flask with an air condenser and a stirring bar. Add compound 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) followed by addition of anhydrous dichloroethane (15 ml). The reaction mixture was sparged with Ar for 30 min, then TFA (3 drops) was added. The reaction solution was heated up to 40 °C overnight. After cooling the reaction down to 0 °C in an ice-water bath, p-chloranil (200.0 mg, 0.8 mmol) was added. The reaction was maintained at 0°C for 20 minutes. Then BF ₃ •OEt ₂ (0.8 mL, 6.5 mmol) and Et ₃ N (0.5 mL, 3.6 mmol) were added at 0°C. The reaction mixture was heated up to 50 °C for 2 hours. The reaction mixture was loaded on silica gel and purified by flash chromatography using DCM in hexane (0 to 80% to 90%) as eluent to give pure BODIPY PLC-8.3 as a dark purple solid, 162.5 mg, 48% yield Rate. MS ₍ APCI): Calcd. for _C35H30BF2N2O ([MH] ^- ) = _{543 Found} : 543. ¹ H NMR (400 MHz, CDCl ₃ ) 8.08 (d, J = 7.2 Hz, 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).

General procedure for PLC-8 : Install a 10 mL vial with a stir bar. Add compound 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) in this vial, Then dry DCM (1.5 ml) was added. The reaction mixture was heated up to 40 °C overnight. After cooling the reaction down to room temperature, the reaction mixture was loaded on silica gel and purified by flash chromatography using EtOAc in DCM (0 to 5%) as eluent to give pure RL-naphthalene as a dark purple solid Imide-BODIPY PLC-8 . The solid was further triturated with MeOH (10 ml) to give RL-naphthylimide-BODIPY PLC-8 , 31.0 mg, 69% yield. MS (APCI) _{: Calcd} . for _{C63H47BF2N3O5} ([MH] ^- ) = ₉₇₅ Found: ₉₇₅ . ¹ H NMR (400 MHz, CDCl ₃ ) 8.66 (dd, J = 18.4 Hz, 7.6 Hz, 2H), 8.10 (td, J = 8.0 Hz, 1.6 Hz, 2H), 8.08 (bs, 1H), 7.99 (d , J = 8.0 Hz, 1H), 7.56 (ddd, J = 8.0 Hz, 8.0 Hz, 1.6 Hz, 1H), 7.36 (m, 11H), 7.22 (dd, J = 7.2 Hz, 2.0 Hz, 2H), 6.95 (s, 2H), 6.43 (s, 2H) 2.88 (t, J = 7.2 Hz, 2H), 2.70 (t, J = 7.2 Hz, 2H), 2.62 (m, 4H), 2.29 (s, 6H), 2.20 (m, 6H), 2.02 (ddd, J = 6.8 Hz, 6.8 Hz, 6.8 Hz, 4H).

Synthesis of PLC-9 : General procedure for PLC-9 : Install a 10 mL vial with a stir bar. Add compound 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) in this vial, Then dry DCM (1.5 ml) was added. The reaction mixture was heated up to 40 °C overnight. After cooling the reaction down to room temperature, the reaction mixture was loaded on silica gel and purified by flash chromatography using EtOAc in DCM (0 to 5%) as eluent to give pure RL-naphthylamide as a dark green solid Imine-BODIPY PLC-9 . The solid was further triturated with MeOH (10 ml) to give RL-naphthylimide-BODIPY PLC-9 , 25.0 mg, 54% yield. MS (APCI) _{: Calcd} . for _{C6iH43BF2N3O5} ([MH] ^- ) = ₉₄₇ Found: ₉₄₇ . ¹ H NMR (400 MHz, CDCl ₃ ) 8.67 (dd, J = 18.4 Hz, 7.6 Hz, 2H), 8.10 (m, 3H), 7.99 (d, J = 8.0 Hz, 1H), 7.56 (ddd, J = 8.0 Hz, 8.0 Hz, 1.6 Hz, 1H), 7.34 (m, 11H), 7.23 (m, 2H), 6.95 (m, 2H), 2.88 (t, J = 7.2 Hz, 2H), 2.70 (t, J = 7.2 Hz, 2H), 2.62 (m, 4H), 2.29 (s, 6H), 2.20 (ddd, J = 7.6 Hz, 7.6 Hz, 7.6 Hz, 6H), 2.24 (ddd, J = 7.6 Hz, 7.6 Hz , 7.6 Hz, 2H).

Synthesis of PLC-10 : General procedure for PLC-10 : Install a 10 mL vial with a stir bar. Add compound 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) in this vial, Then dry DCM (1.5 ml) was added. The reaction mixture was heated up to 40 °C overnight. After cooling the reaction down to room temperature, the reaction mixture was loaded on silica gel and purified by flash chromatography using EtOAc in DCM (0 to 5%) as eluent to give pure RL-naphthylidene as a dark purple solid Amine - BODIPY PLC-10 . The solid was further triturated with MeOH (10 ml) to give RL-naphthylimide-BODIPY PLC-10 , 51.0 mg, 94% yield. MS _{( APCI} ) _: Calcd. for _{C63H48BF2N3O4S} ([MH] ^- ) = 991 Found _: 991. ¹ H NMR (400 MHz, CDCl ₃ ) 8.68 (d, J = 8.0 Hz, 1H), 8.48 (d, J = 8.0 Hz, 1H), 8.26 (m, 2H), 8.09 (m, 2H), 7.56 ( d, J = 8.0 Hz, 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 = 7.6 Hz, 2H), 2.70 (t, J = 7.6 Hz, 2H), 2.62 (m, 4H), 2.29 (s, 6H), 2.20 (m, 6H), 2.24 (ddd, J = 6.8 Hz, 6.8 Hz, 6.8 Hz, 4H).

Synthesis of PLC-11: General procedure for PLC-11 : Install a 10 mL vial with a stir bar. Add compound 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) in this vial, Then dry DCM (1.5 ml) was added. The reaction mixture was heated up to 40 °C overnight. After cooling the reaction down to room temperature, the reaction mixture was loaded on silica gel and purified by flash chromatography using EtOAc in DCM (0 to 5%) as eluent to give pure RL-naphthylamide as a dark green solid Imine-BODIPY PLC-11 . The solid was further triturated with MeOH (10 ml) to give RL-naphthylimine-BODIPY PLC-11 , 40.0 mg, 72% yield. MS ₍ APCI) _{: Calcd} . for _{C6iH44BF2N3O4S} ([MH] ^- ) = 963 _Found : 963. ¹ H NMR (400 MHz, CDCl ₃ ) 8.81 (d, J = 8.0 Hz, 2H), 8.68 (d, J = 8.0 Hz, 1H), 8.48 (d, J = 8.0 Hz, 1H), 8.26 (m, 2H), 7.56 (d, J = 8.0 Hz, 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).

Synthesis of PLC-12 : General procedure for PLC-12 : Install a 10 mL vial with a stir bar. Add compound 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) in this vial, Then dry DCM (1.5 ml) was added. The reaction mixture was heated up to 40 °C overnight. After cooling the reaction down to room temperature, the reaction mixture was loaded on silica gel and purified by flash chromatography using EtOAc (0 to 5%) with DCM as eluent to give pure RL-naphthoyl as a dark green solid Imine-BODIPY PLC-12 . The solid was further triturated with MeOH (10 ml) to give RL-naphthylimine-BODIPY PLC-12 , 31.0 mg, 61% yield. MS ( _{APCI )} : _{Calcd . for C59H38BCl2F2N3O4S} ([M+H] ⁺ ) = 1005 Found: 1005. ¹ H NMR (400 MHz, CDCl ₃ ) 8.81 (m, 2H), 8.68 (d, J = 8.0 Hz, 1H), 8.48 (d, J = 8.0 Hz, 1H), 8.26 (m, 2H), 7.56 ( d, J = 8.0 Hz, 1H), 7.43 (m, 7H), 7.31 (m, 6H), 7.25 (m, 2H), 6.37 (s, 2H), 2.93 (m, 4H), 2.87 (d, J = 7.6 Hz, 2H), 2.69 (m, 6H), 2.24 (s, 6H), 2.19 (ddd, J = 7.6 Hz, 7.6 Hz, 7.6 Hz, 2H).

Synthesis of PLC-13 : General procedure for PLC-13 : Install a 10 mL vial with a stir bar. Add compound 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) in this vial, Then dry DCM (1.5 ml) was added. The reaction mixture was heated up to 40 °C overnight. After cooling the reaction down to room temperature, the reaction mixture was loaded on silica gel and purified by flash chromatography using EtOAc (0 to 5%) with DCM as eluent to give pure RL-naphthoyl as a dark green solid Imine-BODIPY PLC-13 . The solid was further triturated with MeOH (10 ml) to give RL-naphthylimine-BODIPY PLC-13 , 29.0 mg, 52% yield. _{MS ( APCI} ): _Calcd . for _{C6iH44BF2N3O4S} ([MH] ^- ) = 963 Found: 963. ¹ H NMR (400 MHz, CDCl ₃ ) 8.81 (m, 2H), 8.68 (d, J = 8.0 Hz, 1H), 8.48 (d, J = 8.0 Hz, 1H), 8.26 (m, 2H), 7.56 ( d, J = 8.0 Hz, 1H), 7.43 (m, 9H), 7.29 (m, 6H), 7.24 (m, 2H), 2.88 (m, 6H), 2.72 (t, J = 7.2 Hz, 2H), 2.54 (m, 4H), 2.21 (ddd, J = 7.2 Hz, 7.2 Hz, 7.2 Hz, 2H).

Synthesis of PLC-14 : General procedure for PLC-14 : Install a 10 mL vial with a stir bar. Add compound 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) in this vial, Then dry DCM (1.5 ml) was added. The reaction mixture was heated up to 40 °C overnight. After cooling the reaction down to room temperature, the reaction mixture was loaded on silica gel and purified by flash chromatography using EtOAc (0 to 5%) with DCM as eluent to give pure RL-naphthoyl as a dark green solid Imine-BODIPY PLC-14 . The solid was further triturated with MeOH (10 ml) to give RL-naphthylimine-BODIPY PLC-14 , 44.0 mg, 80% yield. MS (APCI): Calcd. for C ₆₁ H ₄₄ BF ₂ N ₃ O ₆ S ([MH] ⁻ ) = 995 found 995. ¹ H NMR (400 MHz, CDCl ₃ ) 8.81 (m, 2H), 8.68 (d, J = 8.0 Hz, 1H), 8.48 (d, J = 8.0 Hz, 1H), 8.26 (m, 2H), 7.56 ( d, J = 8.0 Hz, 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 = 7.6 Hz, 7.6 Hz, 7.6 Hz, 2H).

Synthesis of PLC-15 : General procedure for PLC-15 : Install a 10 mL vial with a stir bar. Add compound 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) in this vial, Then dry DCM (1.5 ml) and THF (1.5 ml) were added. The reaction mixture was heated up to 60 °C overnight. After cooling the reaction down to room temperature, the reaction mixture was loaded on silica gel and purified by flash chromatography using EtOAc (0 to 5%) with DCM as eluent to give pure RL-naphthoyl as a dark green solid Imine-BODIPY PLC-15 . The solid was further triturated with MeOH (10 ml) to give RL-naphthylimide-BODIPY PLC-15 , 6.0 mg, 16% yield. MS _{(APCI): Calcd. for C67H52BF2N3O5 ( [ MH} ] ^- ) = 1027 Found _: 1027. ¹ H NMR (400 MHz, CDCl ₃ ) 8.68 (d, J = 8.0 Hz, 1H), 8.64 (d, J = 8.0 Hz, 1H), 8.30 (m, 2H), 8.11 (dd, J = 8.0 Hz, J = 1.6 Hz, 1H), 7.99 (d, J = 8.0 Hz, 1H), 7.56 (td, J = 8.0 Hz, J = 1.6 Hz, 1H), 7.41 (m, 10H), 7.31 (m, 3H) , 7.00 (s, 2H), 6.19 (s, 2H), 2.89 (t, J = 7.6 Hz, 2H), 2.71 (t, J = 7.6 Hz, 2H), 2.51 (s, 6H), 2.21 (m, 2H), 1.98 (m, 16H).

Synthesis of PLC-16 : General procedure of PLC-16.3 : Install an air condenser and a stirring bar in a 100 mL 2-neck round bottom flask. Add compound 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) followed by addition of anhydrous dichloromethane (20 ml). The reaction mixture was sparged with Ar for 30 min, then p-TsOH•H ₂ O (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 maintained at room temperature for 1 hour. Then _Et3N (1.2 mL, 8.40 mmol) was added and the reaction was kept at room temperature for 30 minutes, followed by the addition of _BF3 • _OEt2 (2.1 mL, 12.6 mmol) at room temperature. The reaction mixture was kept at room temperature for another 1 hour. The reaction mixture was loaded on silica gel and purified by flash chromatography using DCM in hexane (0 to 80% to 90%) as eluent to give pure BODIPY PLC-16.3 as a blue-golden solid, 279.0 mg, 36% Yield. MS ₍ APCI): _Calcd . for _C33H25BF4N2O ([MH] ^- ) ₌ 552 Found: 552.

General procedure for PLC-16 : Install a 10 mL vial with a stir bar. Add compound 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) in this vial, Then dry DCM (1.5 ml) was added. The reaction mixture was heated up to 40 °C overnight. After cooling the reaction down to room temperature, the reaction mixture was loaded on silica gel and purified by flash chromatography using EtOAc in DCM (0 to 5%) as eluent to give pure RL-naphthoyl as a green-purple solid Imine-BODIPY PLC-16 . The solid was further triturated with MeOH (10 ml) to give RL-naphthylimine-BODIPY PLC-16 , 25.0 mg, 47% yield. MS ₍ APCI) _{: Calcd} . for _{C6iH42BF4N3O5} ([MH] ^- ) = ₉₈₃ Found: 983. ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) 8.65 (d, J = 8.0 Hz, 1H), 8.61 (d, J = 8.0 Hz, 1H), 8.13 (dd, J = 8.0 Hz, J = 1.6 Hz, 1H), 8.02 (m, 3H), 7.60 (td, J = 8.0 Hz, J = 1.6 Hz, 1H), 7.39 (m, 13H), 7.04 (m, 2H), 6.63 (s, 2H), 2.91 ( t, J = 7.2 Hz, 2H), 2.77 (t, J = 7.2 Hz, 2H), 2.64 (m, 4H), 2.70 (dd, J = 6.8 Hz, J = 6.8 Hz, 6H), 2.20 (m, 9H).

Synthesis of PLC-17 : General procedure of PLC-17.3 : Install an air condenser and a stirring bar in a 100 mL 2-neck round bottom flask. To this flask was added compound 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), followed by the addition of anhydrous dichloromethane (20 ml). The reaction mixture was sparged with Ar for 30 min, then p-TsOH•H ₂ O (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 maintained at room temperature for 1 hour. Then _Et3N (1.2 mL, 8.64 mmol) was added and the reaction was kept at room temperature for 30 minutes, followed by the addition of _BF3 • _OEt2 (1.6 mL, 12.96 mmol) at room temperature. The reaction mixture was kept at room temperature for another 1 hour. The reaction mixture was loaded on silica gel and purified by flash chromatography using DCM in hexane (0 to 80% to 90%) as eluent to give pure BODIPY PLC-17.3 as a brown-golden solid, 211.0 mg, 28% Yield. MS ₍ APCI): _Calcd . for _C31H21BF4N2O ([MH] ⁻ ) ₌ 524 Found: 524. ¹ H NMR (400 MHz, CDCl ₃ ) 8.80 (d, J = 8.0 Hz, 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).

General procedure for PLC-17 : Install a 10 mL vial with a stir bar. Add compound 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) in this vial, Then dry DCM (1.5 ml) was added. The reaction mixture was heated up to 40 °C overnight. After cooling the reaction down to room temperature, the reaction mixture was loaded on silica gel and purified by flash chromatography using EtOAc in DCM (0 to 5%) as eluent to give pure RL-naphthylamide as a dark green solid Imine-BODIPY PLC-17 . The solid was further triturated with MeOH (10 ml) to give RL-naphthylimide-BODIPY PLC-17 , 38.0 mg, 70% yield. MS ₍ APCI) _{: Calcd} . for _{C59H38BF4N3O5} ([MH] ^- ) = ₉₅₅ Found: 955. ¹ H NMR (400 MHz, CDCl ₃ ) 8.80 (m, 2H), 8.68 (d, J = 8.0 Hz, 1H), 8.64 (d, J = 8.0 Hz, 1H), 8.11 (dd, J = 8.0 Hz, J = 1.6 Hz, 1H), 7.99 (d, J = 8.0 Hz, 1H), 7.56 (td, J = 8.0 Hz, J = 1.6 Hz, 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 = 6.8 Hz, J = 6.8 Hz, 6H), 2.19 (m, 2H).

Synthesis of PLC-18 : General procedure for PLC-18 : Install a 10 mL vial with a stir bar. Add compound 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) in this vial, Then dry DCM (1.5 ml) was added. The reaction mixture was heated up to 40 °C overnight. After cooling the reaction down to room temperature, the reaction mixture was loaded on silica gel and purified by flash chromatography using EtOAc in DCM (0 to 5%) as eluent to give pure RL-naphthylidene as a dark purple solid Amine - BODIPY PLC-18 . The solid was further triturated with MeOH (10 ml) to give RL-naphthylimine-BODIPY PLC-18 , 43.0 mg, 78% yield. MS (APCI) _{: Calcd} . for _{C63H48BF2N3O6S} ([MH] ^- ) = _{1023 Found} : 1023. ¹ H NMR (400 MHz, CDCl ₃ ) 8.68 (d, J = 8.0 Hz, 1H), 8.47 (d, J = 8.0 Hz, 1H), 8.26 (m, 2H), 8.11 (m, 2H), 7.56 ( d, J = 8.0 Hz, 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 = 7.2 Hz, 2H), 2.71 (t, J = 7.2 Hz, 2H), 2.62 (m, 4H), 2.28 (m, 6H), 2.02 (ddd, J = 7.2 Hz, J = 7.2 Hz, J = 7.2 Hz, 4H).

Synthesis of PLC-19 : General procedure for PLC-19 : Install a 10 mL vial with a stir bar. Add compound 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) in this vial, Then dry DCM (1.5 ml) was added. The reaction mixture was heated up to 40 °C overnight. After cooling the reaction down to room temperature, the reaction mixture was loaded on silica gel and purified by flash chromatography using EtOAc in DCM (0 to 5%) as eluent to give pure RL-naphthalene as a dark blue-green solid Amide-BODIPY PLC-19 . The solid was further triturated with MeOH (10 ml) to give RL-naphthylimide-BODIPY PLC-19 , 43.0 mg, 78% yield. MS (APCI): _Calcd . for _{C59H38BF4N3O4S} ([MH] ^- ) _{= 971 Found} : 971. ¹ H NMR (400 MHz, CDCl ₃ ) 8.80 (m, 2H), 8.67 (d, J = 8.0 Hz, 1H), 8.47 (d, J = 8.0 Hz, 1H), 8.25 (m, 2H), 7.56 ( d, J = 8.0 Hz, 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 = 7.6 Hz, J = 7.6 Hz, J = 7.6 Hz, 4H).

Synthesis of PLC-20 : General procedure for PLC-20 : Install a 10 mL vial with a stir bar. Add compound 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) in this vial, Then dry DCM (1.5 ml) was added. The reaction mixture was heated up to 40 °C overnight. After cooling the reaction down to room temperature, the reaction mixture was loaded on silica gel and purified by flash chromatography using EtOAc in DCM (0 to 5%) as eluent to give pure RL-naphthalene as a dark blue-green solid Imide-BODIPY PLC-20 . The solid was further triturated with MeOH (10 ml) to give RL-naphthylimide-BODIPY PLC-20 , 30.0 mg, 56% yield. MS ₍ APCI) _{: Calcd} . for _{C6iH42BF4N3O4S} ([MH] ^- ) = ₉₉₉ Found: 999. ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) 8.65 (d, J = 8.0 Hz, 1H), 8.44 (d, J = 8.0 Hz, 1H), 8.28 (m, 2H), 8.03 (m, 2H), 7.61 (d, J = 8.0 Hz, 1H), 7.47 (m, 5H), 7.33 (m, 8H), 7.04 (m, 2H), 6.63 (s, 2H), 2.91 (t, J = 7.2 Hz, 2H ), 2.76 (t, J = 7.2 Hz, 2H), 2.64 (m, 4H), 2.35 (bs, 3H), 2.13 (m, 6H).

Synthesis of PLC-21 : General procedure for PLC-21 : Install a 10 mL vial with a stir bar. Add compound 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) in this vial, Then dry DCM (1.5 ml) was added. The reaction mixture was heated up to 40 °C overnight. After cooling the reaction down to room temperature, the reaction mixture was loaded on silica gel and purified by flash chromatography using EtOAc in DCM (0 to 5%) as eluent to give pure RL-naphthalene as a dark blue-green solid Amide-BODIPY PLC-21 . The solid was further triturated with MeOH (10 ml) to give RL-naphthylimide-BODIPY PLC-21 , 39.0 mg, 72% yield. MS ₍ APCI _{) :} Calcd. for _{C63H48BF2N3O5} ([MH]-) = ₉₇₅ Found: 975. ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) 8.76 (m, 2H), 8.66 (d, J = 8.0 Hz, 1H), 8.61 (d, J = 8.0 Hz, 1H), 8.13 (dd, J = 8.0 Hz, J = 1.6 Hz, 1H), 8.02 (d, J = 8.0 Hz, 1H), 7.60 (td, J = 8.0 Hz, J = 1.6 Hz, 1H), 7.38 (m, 13H), 7.01 (s, 2H), 2.91 (m, 6H), 2.72 (t, J = 7.2 Hz, 2H), 2.57 (m, 4H), 2.25 (s, 6H), 2.23 (m, 2H), 1.42 (s, 6H).

Synthesis of PLC-22 : General procedure for PLC-22 : Install a 10 mL vial with a stir bar. Add compound 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) in this vial, Then dry DCM (1.5 ml) was added. The reaction mixture was heated up to 40 °C overnight. After cooling the reaction down to room temperature, the reaction mixture was loaded on silica gel and purified by flash chromatography using EtOAc in DCM (0 to 5%) as eluent to give pure RL-naphthalene as a dark blue-green solid Amide-BODIPY PLC-22 . The solid was further triturated with MeOH (10 ml) to give RL-naphthylimine-BODIPY PLC-22 , 33.0 mg, 63% yield. MS ₍ APCI) _: Calcd. for _{C6iH44BF2N3O5} ([MH] ^- ) = ₉₄₇ Found: ₉₄₇ . ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) 8.67 (d, J = 8.0 Hz, 1H), 8.62 (d, J = 8.0 Hz, 1H), 8.14 (dd, J = 8.0 Hz, J = 1.6 Hz, 1H), 8.05 (m, 2H), 8.02 (d, J = 8.0 Hz, 1H), 7.66 (m, 2H), 7.60 (td, J = 8.0 Hz, J = 1.6 Hz, 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).

Synthesis of PLC-23 : General procedure for PLC-23 : Install a 10 mL vial with a stir bar. Add compound 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) in this vial, Then dry DCM (1.5 ml) was added. The reaction mixture was heated up to 40 °C overnight. After cooling the reaction down to room temperature, the reaction mixture was loaded on silica gel and purified by flash chromatography using EtOAc in DCM (0 to 5%) as eluent to give pure RL-naphthalene as a dark blue-green solid Imide-BODIPY PLC-23 . The solid was further triturated with MeOH (10 ml) to give RL-naphthylimide-BODIPY PLC-23 , 17.0 mg, 34% yield. MS _{( APCI} ) _: Calcd. _{for C59H38BCl2F2N3O5} ([MH] ^- ) = 988 Found: ₉₈₈ . ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) 8.67 (d, J = 8.0 Hz, 1H), 8.62 (d, J = 8.0 Hz, 1H), 8.14 (dd, J = 8.0 Hz, J = 1.6 Hz, 1H), 8.05 (m, 2H), 8.03 (d, J = 8.0 Hz, 1H), 7.65 (m, 2H), 7.60 (td, J = 8.0 Hz, J = 1.6 Hz, 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).

Synthesis of PLC-24 : General procedure for PLC-24 : 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) contained in DCM (5 mL) ) and DMAP/p-TsOH (8 mg, 0.027 mmol) 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% à 100% DCM), then DCM/ethyl acetate (0% à 5% ethyl acetate). The predominantly red fractions were collected and concentrated under reduced pressure. The resulting solid was triturated with methanol, filtered and dried in air to give a dark red solid (18 mg, 64.6% yield). LCMS ₍ APCI-): Calcd. _{for C61H42BCl2F2N3O4S} (M-) _{= 1031.23} ; found _: 1031. ¹ H NMR (400 MHz, d ₂ -TCE) δ 8.56 (d, J = 8.2 Hz, 1H), 8.35 (d, J = 8.0 Hz, 1H), 8.19 (dd, J = 8.8, 4.5 Hz, 2H) , 7.97 (s, 2H), 7.51 (d, J = 8.0 Hz, 1H), 7.38 (dt, J = 7.3, 2.4 Hz, 5H), 7.29 (d, J = 9.3 Hz, 6H), 7.24 - 7.15 ( m, 4H), 6.40 (s, 2H), 2.82 (t, J = 7.5 Hz, 2H), 2.67 (t, J = 7.4 Hz, 2H), 2.54 (d, J = 6.8 Hz, 4H), 2.24 ( s, 4H), 2.11 (td, J = 13.4, 11.8, 5.9 Hz, 2H), 2.04 - 1.89 (m, 4H).

Synthesis of PLC-25 : General procedure for PLC-25 : Compound PLC-2.1 (16 mg, 0.034 mmol), compound Ex-5 (27 mg, 0.051 mmol), EDC·HCl (60 mg, 0.31 mmol) in DCM (4 mL) ) and DMAP/p-TsOH (8.8 mg, 0.03 mmol) was stirred overnight at room temperature. The resulting mixture was then loaded onto silica gel and purified by flash chromatography using the eluent of DCM/ethyl acetate (0%→10% ethyl acetate). The main red fractions were collected and concentrated under reduced pressure to 0.5 mL, then 10 mL of methanol was added. The resulting precipitate was filtered and air dried to give a dark red solid (23 mg, 62% yield). LCMS _{(APCI-): Calcd. for C69H44BCl2F8N3O5 ( M- ) = 1227.26} ; found: 1227. ¹ H NMR (400 MHz, d ₂ -TCE) δ 8.58 (dd, J = 19.5, 8.1 Hz, 2H), 8.18 (d, J = 2.2 Hz, 1H), 8.06 (d, J = 8.1 Hz, 1H) , 8.02 (d, J = 1.5 Hz, 2H), 7.97 (t, J = 4.6 Hz, 2H), 7.87 (s, 1H), 7.72 (dd, J = 8.6, 2.1 Hz, 1H), 7.49 (d, J = 8.6 Hz, 1H), 7.39 (d, J = 8.2 Hz, 2H), 7.34 (d, J = 8.3 Hz, 1H), 7.32 - 7.25 (m, 6H), 7.25 - 7.18 (m, 4H), 6.40 (s, 2H), 2.82 (t, J = 7.5 Hz, 2H), 2.67 (t, J = 7.4 Hz, 2H), 2.61 - 2.50 (m, 4H), 2.24 (s, 4H), 2.13 (q , J = 7.4 Hz, 2H), 2.04 - 1.90 (m, 4H).

Synthesis of PLC-26 : Compound PLC-26.1 (6-(4-(tert-butyl)-2-nitrophenoxy)-1H,3H-benzo[de]isomethanol-1,3-dione): Add to 1L 2N A round bottom flask was placed with a stir bar and placed in an aluminum heating block. The flask was fitted with a finned condenser, gas adapter and flow controller. The flask was flushed with argon. To the flask was added 6-bromo-1H,3H-benzo[de]isomethan-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 complete reaction. The reaction mixture was cooled to room temperature. 1N HCl (44 mL) and water (175 mL) were added to the flask. After stirring for about 15 minutes, the resulting precipitate was filtered off and washed with water. The dried precipitate was dissolved in warm ethyl acetate and filtered warm to remove a small amount of insoluble material. Ethyl acetate was removed in vacuo. The resulting solid was triturated with hot methanol, then allowed to cool to room temperature. The resulting precipitate was filtered off and washed with methanol. The solid was dried in a vacuum oven at 100°C. Obtained 8.18 g (52% yield). MS (APCI): calcd for _C22H17NO6 (M+H) _{= 392} ; found: 392. ¹ H NMR (400 MHz, tetrachloroethane-d ₂ ) 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).

Compound PLC-26.2 (6-(2-Amino-4-(tert-butyl)phenoxy)-1H,3H-benzo[de]isomethanol-1,3-dione): Add to 250 mL Put a stirring rod in a 2N round bottom flask and install a finned condenser, gas adapter and flow controller. Place the flask in an aluminum heating block. The flask was flushed with argon. To the flask was added compound PLC-26.1 (10.0 mmol, 3.914 g) and SnCl ₂ .2H ₂ O (40.0 mmol, 9.024 g), 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 time TLC showed complete conversion to product. The reaction mixture was cooled to room temperature, then the pH was adjusted to pH ~8 with 2N NaOH. The resulting precipitate was filtered off. The solid was extracted with 2-methyl THF (8 X 100 mL). The layers were separated, 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) _: calcd for _C22H19NO4 (M+H) = 362; found: ₃₆₂ . ¹ H NMR (400 MHz, tetrachloroethane-d ₂ ) δ 8.88 (dd, J = 8.4, 1.2 Hz, 1H), 8.69 (dd, J = 7.3, 1.2 Hz, 1H), 8.48 (d, J = 8.4 Hz, 1H), 7.89 (dd, J = 8.4, 7.3 Hz, 1H), 7.03 - 6.93 (m, 3H), 6.88 (dd, J = 8.4, 2.3 Hz, 1H), 1.35 (s, 9H).

Compound PLC-26.3 (9-(tertiary butyl)-1H,3H-iso[6,5,4-mna]𠮿 -1,3-diketone): Into a 40 mL vial was placed NaNO ₂ (30.0 mmol, 2.070 g), water (10 mL) and a stir bar. Place the vial in an ice water bath and stir to dissolve. Put a stirring bar and compound PLC-26.2 (4.00 mmol, 1.446 g), hydrochloric acid (37%) (20.0 mmol, 12.1M, 1.65 mL) and glacial acetic acid (30 mL) into a 100 mL round bottom flask. The flask was lowered into an ice water bath and stirred for about 1 minute, then the sodium nitrite solution was added in small portions over a period of 3 minutes. The solution was stirred for 1 hour in an ice-water bath. A 1 L 2N round bottom flask was clamped with the neck off center at an angle such that the dropping funnel inserted into the neck would drop above the stirring vortex. Fit the other neck to the finned condenser. To this flask was added a large stir bar, CuSO ₄ .5H ₂ O (27.4 mmol, 6.842 g) and water (80 mL). Near the end of the one hour waiting period for the diazonium salt, the copper(II) solution was placed in an aluminum heating 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 diazonium solution was added dropwise over a period of 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 on silica gel in vacuo. Purified by column chromatography on silica gel (220 g, equilibrated 50% hexane/DCM, eluting 50% (2 CV) to 100% DCM (20 CV), isocratic DCM (15 CV) to 0% EtOAc /DCM (0 CV) to 1% EtOAc/DCM (10 CV)). Product smears. All fractions bearing product were collected and evaporated to dryness in vacuo. Obtained 528 mg (38% yield). MS (APCI): Calcd. for _C22H16O4 (M+H) = 345; found _{: 345} . ¹ H NMR (400 MHz, tetrachloroethane-d ₂ ) δ 8.61 (d, J = 7.9 Hz, 1H), 8.56 (d, J = 8.4 Hz, 1H), 8.05 (d, J = 2.2 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).

Compound PLC-26.4 (4-(4-(9-(tert-butyl)-1,3-two-side oxy-1H-𠮿 and[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)butanoic acid): Into 100 mL of 2N RBF with stir bar and finned condenser, gas aptamer and 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. The heat block was set to 175°C and the reaction was heated and stirred for 6.5 hours, 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 argon flow. Obtained 738 mg (96% yield). MS (APCI): Calcd. for _C32H27NO5 (M+H) = 506; found _{: 506} . ¹ H NMR (400 MHz, DMSO-d ₆ ) 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).

Compound PLC-26 4-(4-(9-(tert-butyl)-1,3-dioxo-1H-𠮿 And[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)butanoic acid (3,5-dichloro-4-(19,19-difluoro-6,7,11, 12,13,19-Hexahydro-5H-18l4,19l4-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 ester): to Put a stirring bar, 3,5-dichloro-4-(19,19-difluoro-6,7,11,12,13,19-hexahydro-5H-18l4,19l4-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), followed by anhydrous DCM (10 mL). The vial was capped and stirred at room temperature for 4.5 hours. The reaction mixture was diluted with hexanes (to about 35 mL) and loaded onto a solids loading cartridge (about 20 g _Si02 ). The reaction mixture was purified by column chromatography on silica gel (120 g, equilibrate 100% toluene, elute 100% (5 CV) to 5% EtOAc/toluene (30 CV)). Fractions containing product were evaporated to dryness and repurified by flash chromatography on silica gel (solids load, 120 g column, equilibrated 40% DCM/hexane, eluting 40% (2 CV) to 100% DCM ( 10 CV) to isoconcentration DCM until the compound is completely eluted)). Fractions containing product were evaporated to dryness in vacuo. Obtained 19.8 mg (37% yield). MS (APCI _{) : Calcd} . _{for C65H50BCl2F2N3O5} (M-) = 1071; found ₁₀₇₁ . ¹ H NMR (400 MHz, methylene chloride-d ₂ ) 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), 7.38 - 7.24 (m, 10H), 6.51 (s, 2H), 2.90 (t, J = 7.6 Hz, 2H), 2.75 (t, J = 7.4 Hz, 2H), 2.64 (t, J = 6.8 Hz, 4H), 2.43 - 2.26 (m, 4H), 2.21 (p, J = 7.5 Hz, 2H), 2.05 (p, J = 7.0 Hz, 4H), 1.44 (s, 9H).

Synthesis of PLC-27 : Compound PLC-27.2 (2-(4-(9-(tert-butyl)-1,3-dioxo-1H-𠮿 [2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid): compound PLC-27.2 was obtained 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 ): calcd for _C30H23NO5 (M+H) = 478; found: ₄₇₈ . ¹ H NMR (400 MHz, DMSO-d ₆ ) δ 8.48 (d, J = 7.9 Hz, 1H), 8.44 (d, J = 8.3 Hz, 1H), 8.38 (d, J = 8.1 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).

Compound PLC-27 2-(4-(9-(tert-butyl)-1,3-dioxo-1H-𠮿 And[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid (3,5-dichloro-4-(19,19-difluoro-6,7,11,12 ,13,19-Hexahydro-5H-18l4,19l4-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 ester): compound PLC -27 is derived from 3,5-dichloro-4-(19,19-difluoro-6,7,11,12,13,19-hexahydro-5H-18l4,19l4-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 (0.100 mmol, 58.6 mg), compound 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) for synthesis. The vial was capped and stirred overnight at room temperature. The next day, more compound EDC.HCl (0.200 mmol, 38.8 mg) was added and stirred at room temperature for 90 minutes. More EDC.HCl (0.200 mmol, 38.3 mg) was added and stirring was continued 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 (solids load, 120 g column, equilibrated 40% DCM/hexane, eluting 40% (2 CV) to 100% DCM (10 CV) to isocratic DCM until the compound is completely dissolved)). Fractions containing product were evaporated to dryness in vacuo. Obtained 11.0 mg (11% yield). MS (APCI) _: Calcd. _{for C63H46BCl2F2N3O5} (M-) = 1043; _{found : 1043} . ¹ H NMR (400 MHz, methylene chloride-d ₂ ) δ 8.67 (d, J = 7.9 Hz, 1H), 8.60 (d, J = 8.4 Hz, 1H), 8.13 (d, J = 2.3 Hz, 1H ), 8.07 (d, J = 8.0 Hz, 1H), 8.00 (d, J = 6.9 Hz, 2H), 7.64 (dd, J = 8.8, 2.3 Hz, 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 = 7.1 Hz, 4H), 1.44 (s, 9H).

Synthesis of compound PLC-28 Compound PLC-28.2 2-(4-(9- bromo -1,3- dioxo -1H- 𠮿 [2,1,9-def] isoquinolin -2(3H)-yl ) phenyl ) acetic acid: PLC-28.1 (400.0 mg, 1.1 mmol), 4- amine in DMF (8 mL) A mixture of phenylphenylacetic acid (329.4 mg, 2.2 mmol) and DMAP (9.3 mg, 0.080 mmol) was degassed at room temperature. The mixture was then heated up to 165°C and maintained at this temperature for 3 hours. TLC and LCMS showed about 95% conversion with no observable side reactions. The mixture was cooled down to 50 °C. It was then poured into acetone solution (40 mL), which was precooled by an ice-water bath. The mixture was kept at 0°C for 2 hours and then kept stirring at room temperature overnight. The solid was collected by vacuum filtration and washed by acetone (4 mL). And it was dried by vacuum oven at 100° C. for 3 hours to obtain pure compound PLC-28.2 395.0 mg as a yellow-brown solid, 73% yield. MS (APCI): Calcd. for _C26H14BrNO5 ([M+H] ⁺ ) = 500 Found _{: 500} . ¹ H NMR (400 MHz, CDCl2CDCl2) δ 8.65 (d, J = 8.0 Hz, 1H), 8.62 (d, J = 8.0 Hz, 1H), 8.21 (dd, J = 6.4 Hz, 2.4 Hz, 1H), 7.99 (bs, 1H), 7.95 (t, J = 7.6 Hz, 1H), 7.67 (dd, J = 8.4 Hz, 2.4 Hz, 1H), 7.53 (d, J = 8.0 Hz, 2H), 7.37 (d, J = 8.4 Hz, 1H), 7.32 (m, 3H), 2.94 (s, 2H).

Compound PLC-28.3 – 2-(4-(9-(4- isopropylphenyl )-1,3- dioxo -1H- 𠮿 And [2,1,9-def] isoquinolin -2(3H) _-yl ) phenyl )acetic acid : PLC- 28.2 (175.0 mg, 0.35 mmol), 4- isopropylphenylboronic acid (114.8 mg, 0.70 mmol), Pd(dppf)Cl ₂ (18.0 mg, 0.025 mmol) and K ₂ CO ₃ (130.4 mg, 0.95 mmol) The mixture was degassed at room temperature. The mixture was then heated up to 80°C and kept at this temperature overnight. TLC and LCMS showed the reaction was complete. The mixture was cooled to room temperature. Then it was added 0.1N HCl (75 mL) and EtOAc (75 mL). Once separated by a separatory funnel, the aqueous solution was further extracted with THF (75 mL*3) after it was saturated with NaCl. The combined organic phases were dried over _{anhydrous Na2SO4} , then filtered and concentrated under a rotary evaporator, and purified by silica gel flash chromatography using 0 to 40% EtOAc/DCM with 0.1% TFA as eluent , to obtain PLC-28.3 as a yellow solid, 70.0 mg, 37% yield. MS (APCI): Calculated for _C35H25NO5 ([MH] ^- ) = ₅₃₉ Found: ₅₃₉ . ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) δ 8.66 (d, J = 7.6 Hz, 1H), 8.61 (d, J = 8.4 Hz, 1H), 8.26 (s, 1H), 8.06 (d, J = 8.0 Hz, 1H), 7.79 (dd, J = 8.4 Hz, 2.0 Hz, 1H), 7.45 (m, 11H), 3.81 (s, 2H), 3.01 (quintet, J = 7.2 Hz, 1H), 1.33 (d , J = 7.2 Hz, 6H).

Compound PLC-28 Synthesis: A 25 mL vial was fitted with a stir bar. Add compound 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) to this vial, Then dry DCM (4.4 ml) was added. The reaction mixture was heated up to 40 °C overnight. After cooling the reaction down to room temperature, the reaction mixture was loaded on silica gel and purified by flash chromatography using EtOAc (0 to 4%) in DCM as eluent to give pure RL-naphthalene as a dark blue solid Amide-BODIPY PLC-28 . The solid was further triturated with MeOH (15 ml) to give RL-naphthylimide-BODIPY PLC-28 , 46.0 mg, 55% yield. MS ( _APCI ) _{: Calcd} . for _{C68H48BCl2F2N3O5} ([MH] ^- ) _{= 1106} Found: 1106. ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) 8.67 (d, J = 8.0 Hz, 1H), 8.63 (d, J = 8.0 Hz, 1H), 8.29 (d, J = 2.4 Hz, 1H), 8.11 ( d, J = 8.0 Hz, 1H), 8.05 (m, 2H), 7.81 (dd, J = 8.0 Hz, J = 2.4 Hz, 1H), 7.65 (m, 4H), 7.51 (d, J = 8.0 Hz, 1H), 7.39 (m, 11H), 7.30 (m, 2H), 6.49 (s, 2H), 4.07 (s, 2H), 3.01 (pentet, J = 6.8 Hz, 1H), 2.64 (m, 4H), 2.33 (bs, 3H), 2.06 (m, 4H), 1.33 (d, J = 6.8 Hz, 6H).

Synthesis of compound PLC-29 Compound 29.1 – 2-(4-(1,3- Dioxo -9-(4-( trifluoromethyl ) phenyl )-1H- 𠮿 And [2,1,9-def] isoquinolin -2(3H)-yl ) phenyl ) acetic acid: A 100 mL vial was fitted with a stir bar. To the vial, compound PLC-28.2 (400.0 mg, 0.80 mmol), 4-( trifluoromethyl ) phenylboronic acid in THF/DMF/H ₂ O (22 ml/ 4.4 ml/ 2.2 ml) was added (262.2 mg, 1.6 mmol), Pd(dppf)Cl ₂ (41.0 mg, 0.056 mmol) and K ₂ CO ₃ (298.0 mg, 2.2 mmol) were degassed at room temperature. The reaction mixture was heated up to 80 °C and the reaction was kept at this temperature overnight. TLC was used to monitor the reaction. Upon completion, the reaction was worked up by addition of 0.1N HCl (150 mL) and EtOAc (150 mL). The aqueous phase was further extracted by THF (150 mL*3). The combined organic phases were dried over anhydrous Na ₂ SO ₄ , concentrated under rotary evaporator and purified by flash chromatography using EtOAc (0 to 40% with 0.1% TFA) in DCM as eluent to give Pure RL-Naphthoimide derivative PLC-29.1 as a yellow/yellow-brown solid. 363.0 mg, 80% yield. MS (APCI): _Calcd . for _C33H18F3NO5 ([M+H] ⁺ ) = 566 Found _{: 566} . ¹ H NMR (400 MHz, DMSO-d ₆ ) 8.76 (m, 1H), 8.56 (m, 2H), 8.52 (dd, J = 8.0 Hz, J = 3.2 Hz, 1H), 8.15 (m, 2H), 8.06 (m, 1H), 7.94 (d, J = 8.0 Hz, 2H), 7.66 (dd, J = 8.0 Hz, J = 4.0 Hz, 1H), 7.53 (m, 1H), 7.45 (d, J = 8.0 Hz, 2H), 7.33 (d, J = 8.0 Hz, 2H), 3.72 (s, 2H).

Compound PLC-29 : A 25 mL vial was fitted with a stir bar. Add 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) to this vial, Then dry DCM (4 ml) was added. The reaction mixture was heated up to 40 °C overnight. After cooling the reaction down to room temperature, the reaction mixture was loaded on silica gel and purified by flash chromatography using EtOAc in DCM (0 to 4%) as eluent to give pure RL-naphthalene as a dark blue solid Imide-BODIPY PLC-29 . The solid was further triturated with MeOH (15 ml) to give RL-naphthylimide-BODIPY PLC-29 , 46.0 mg, 60% yield. MS _{( APCI} ) _: Calcd _{. for C66H41BCl2F5N3O5 (} [MH] ^- ) = 1132 Found _: 1132. ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) 8.69 (d, J = 8.0 Hz, 1H), 8.65 (d, J = 8.0 Hz, 1H), 8.30 (d, J = 2.0 Hz, 1H), 8.11 ( d, J = 8.0 Hz, 1H), 8.06 (m, 2H), 7.82 (m, 5H), 7.65 (m, 2H), 7.55 (d, J = 8.0 Hz, 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).

Synthetic compound PLC-30 Compound PLC-30.1 —2-(4-(9-(3,5- bis ( trifluoromethyl ) phenyl )-1,3- dioxo -1H- 𠮿 And [2,1,9-def] isoquinolin -2(3H)-yl ) phenyl ) acetic acid: A 100 mL vial was fitted with a stir bar. To this vial, compound PLC-28.2 (400.0 mg, 0.80 mmol), 3,5- bis ( trifluoromethyl ) in THF/DMF/H ₂ O (22 ml/ 4.4 ml/ 2.2 ml) was added Phenylboronic acid (262.2 mg, 1.6 mmol), Pd(dppf) _Cl2 (41.0 mg, 0.056 mmol) and _K2CO3 ( _412.6 mg, 2.2 mmol) were degassed at room temperature. The reaction mixture was heated up to 80 °C and the reaction was kept at this temperature overnight. TLC was used to monitor the reaction. Upon completion, the reaction was worked up by addition of 0.1N HCl (150 mL) and EtOAc (150 mL). The aqueous phase was further extracted by THF (150 mL*3). The combined organic phases were dried over anhydrous Na ₂ SO ₄ , concentrated under rotary evaporator and purified by flash chromatography using EtOAc (0 to 40% with 0.1% TFA) in DCM as eluent to give Pure RL-Naphthoimide derivative PLC-30.1 as yellow/yellow-brown solid. 311.0 mg, 61% yield. MS (APCI ₎ : _Calcd . for _C34H17F6NO5 ([M+H] ⁺ ) = 634 Found _: 634. ¹ H NMR (400 MHz, DMSO-d ₆ ) 8.73 (m, 1H), 8.46 (m, 5H), 8.10 (m, 2H), 7.57 (m, 1H), 7.42 (d, J = 8.0 Hz, 2H ), 7.40 (m, 1H), 7.30 (d, J = 8.0 Hz, 2H), 3.72 (s, 2H).

Compound PLC-30 : A 25 mL vial was fitted with a stir bar. Add 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) in this vial, Then dry DCM (4 ml) was added. The reaction mixture was heated up to 40 °C overnight. After cooling the reaction down to room temperature, the reaction mixture was loaded on silica gel and purified by flash chromatography using EtOAc in DCM (0 to 4%) as eluent to give pure RL-naphthalene as a dark blue solid Imide-BODIPY PLC-30 . The solid was further triturated with MeOH (15 ml) to give RL-naphthylimide-BODIPY PLC-30 , 76.0 mg, 93% yield. MS ₍ APCI) _{: Calcd} . for _{C67H40BCl2F8N3O5} ([MH] ^- ) = ₁₂₀₀ Found _: 1200. ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) 8.70 (d, J = 8.0 Hz, 1H), 8.66 (d, J = 8.0 Hz, 1H), 8.28 (d, J = 2.0 Hz, 1H), 8.15 ( d, J = 8.0 Hz, 1H), 8.06 (m, 4H), 7.96 (m, 1H), 7.82 (dd, J = 8.0 Hz, J = 2.0 Hz, 1H), 7.65 (m, 2H), 7.58 ( d, J = 8.0 Hz, 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).

Synthesis of compound PLC-31 Compound PLC-31.1 – 2-(4-(9-(4-( tert-butyl ) phenyl )-1,3- dioxo -1H- 𠮿 And [2,1,9-def] isoquinolin -2(3H) _-yl ) phenyl )acetic acid : PLC- 28.2 (175.0 mg, 0.35 mmol), 4- tert-butylphenylboronic acid (124.6 mg, 0.70 mmol), Pd(dppf)Cl ₂ (18.0 mg, 0.025 mmol) and K ₂ CO ₃ (130.4 mg, 0.95 mmol ) mixture was degassed at room temperature. The mixture was then heated up to 80°C and kept at this temperature overnight. TLC and LCMS showed the reaction was complete. The mixture was cooled to room temperature. Then it was added 0.1N HCl (75 mL) and EtOAc (75 mL). Once separated by a separatory funnel, the aqueous solution was further extracted with THF (75 mL*3) after it was saturated with NaCl. The combined organic phases were dried over _{anhydrous Na2SO4} , then filtered and concentrated under a rotary evaporator, and purified by silica gel flash chromatography using 0 to 40% EtOAc/DCM with 0.1% TFA as eluent , to obtain PLC-31.1 as a yellow solid, 76.0 mg, 39% yield. MS (APCI): Calcd. for _C36H27NO5 ([MH] ^- ) ₌ 553 Found _: 553. ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) δ 8.69 (d, J = 8.0 Hz, 1H), 8.64 (d, J = 8.4 Hz, 1H), 8.24 (d, J = 8.4 Hz, 1H), 8.03 (d, J = 8.0 Hz, 1H), 7.76 (dd, J = 8.4 Hz, 2.0 Hz, 1H), 7.53 (m, 7H), 7.33 (m, 4H), 3.77 (s, 2H), 1.40 (s , 9H).

Compound PLC-31 : A 25 mL vial was fitted with a stir bar. Add 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) in this vial, Then dry DCM (4 ml) was added. The reaction mixture was heated up to 40 °C overnight. After cooling the reaction down to room temperature, the reaction mixture was loaded on silica gel and purified by flash chromatography using EtOAc in DCM (0 to 4%) as eluent to give pure RL-naphthalene as a dark blue solid Amide-BODIPY PLC-31 . The solid was further triturated with MeOH (15 ml) to give RL-naphthylimide-BODIPY PLC-31 , 40.0 mg, 52% yield. _MS (APCI) _{: Calcd} . for _{C69H50BCl2F2N3O5} ([MH] ^- ) ₌ 1120 Found: ₁₁₂₀ . ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) 8.69 (d, J = 8.0 Hz, 1H), 8.63 (d, J = 8.0 Hz, 1H), 8.30 (d, J = 2.0 Hz, 1H), 8.11 ( d, J = 8.0 Hz, 1H), 8.06 (m, 2H), 7.82 (dd, J = 8.0 Hz, J = 2.0 Hz, 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).

Synthesis of compound PLC-32 Compound PLC-32.1 General procedure for compound PLC-32.1 : Ex-4.3 (6.3 g, 17.159 mmol, 1 eq) was suspended in 35 mL of anhydrous DMSO, glycine (2.31 g, 30.77 mmol, 1.8 eq) was added to the reaction mixture. The resulting mixture was stirred at 130°C for 1 hour (the mixture did not dissolve), then it was heated to 160°C for 1 hour, LMCMS showed the reaction was complete. After cooling to room temperature, the solid product was filtered, washed with water (250 mL), and then dried in a vacuum oven to obtain 6.5 g of a cyan-yellow solid, yield 90%. ¹ H NMR (400 MHz, DMSO-d ₆ ) δ 8.65 (s, 1H), 8.50 (s, 1H), 8.46 (d, J = 8.2 Hz, 2H), 8.09 (d, J = 8.0 Hz, 2H) , 7.99 (d, J = 8.7 Hz, 1H), 7.87 (d, J = 8.0 Hz, 2H), 7.58 (d, J = 8.6 Hz, 1H), 7.45 (d, J = 8.4 Hz, 1H), 4.71 (s, 2H).

Compound PLC-32.2 General procedure for compound PLC-32.2 : PLC-32.1 (4.24 g, 10.0 mmol, 1 eq) was suspended in 2-MeTHF (150 ml), H ₂ O (5.0 ml), and 4-(para. Tributyl)phenylboronic acid (3.56 g, 20 mmol, 2 eq), _K2CO3 (2.76 g, 20 mmol, 2 eq), Pd ₍ dppf) _Cl2DCM (163.3 mg, 0.2 mmol, 0.02 eq). The reaction mixture was degassed by Vac-Fill argon cycles 3 times, stirred and heated at 95°C under argon atmosphere for 12 hours. After cooling to room temperature, ethyl acetate (150 ml) was added and acidified to pH 4-5 with 1N HCl. The organic layer was washed with water, separated and concentrated. The residue was stirred in DMF (15 ml), filtered to obtain a solid, which was washed with MeOH (50 mL) and dried in a vacuum oven to give 4.1 g of the product as a cyan-yellow solid, 85% yield. MS (APCI): Calcd. for _C20H10BrNO5 ( _MH ) = 423; found: ₄₂₃ . ¹ H NMR (400 MHz, DMSO-d ₆ ) δ 8.33 (d, J = 6.1 Hz, 3H), 8.24 (d, J = 7.9 Hz, 1H), 7.95 (s, 1H), 7.78 (d, J = 8.3 Hz, 1H), 7.70 (d, J = 7.9 Hz, 2H), 7.50 (d, J = 7.9 Hz, 2H), 7.39 (d, J = 8.3 Hz, 1H), 7.29 (d, J = 8.2 Hz , 1H), 4.52 (s, 2H), 2.89 (s, 3H), 2.73 (s, 3H), 2.54 - 2.47 (m, 21H), 1.34 (s, 10H).

Compound PLC-32 General procedure for compound PLC-32 : PLC-32.2 (71.62 mg, 0.15 mmol, 1.5 eq) was suspended in anhydrous DCM (10.0 ml). To the mixture was added PLC-2.1 (58.5 mg, 0.1 mmol, 1 eq), DMAP-pTSA (58.8 mg, 0.2 mmol, 2 eq), EDC.HCl (57.5 mg, 0.3 mmol, 3 eq), and then Stir under argon atmosphere for 5 hours, dilute with DCM (150 ml), filter, wash solid with 50 ml DCM, collect filtrate, load onto 80 g SiO ₂ column, utilize Hex-DCM (1/1), DCM alone, then DCM with 0.5% EA was eluted. The good fractions were concentrated and then washed with MeOH to give 80 mg, 96% yield. MS ( _APCI ) _: Calcd. _{for C63H46BCl2F2N3O5} (M-) = 1044; _{found :} 1044. ¹ H NMR (400 MHz, d ₂ -TCE) δ 8.63 (d, J = 7.9 Hz, 1H), 8.58 (d, J = 8.3 Hz, 1H), 8.20 (d, J = 2.1 Hz, 1H), 8.01 (d, J = 8.1 Hz, 1H), 7.98 - 7.91 (m, 2H), 7.73 (dd, J = 8.7, 2.1 Hz, 1H), 7.59 - 7.51 (m, 2H), 7.49 - 7.44 (m, 2H ), 7.42 (d, J = 8.6 Hz, 1H), 7.38 (s, 2H), 7.32 (d, J = 8.3 Hz, 1H), 7.27 (dt, J = 7.3, 3.7 Hz, 4H), 7.20 (dt , J = 5.1, 3.7 Hz, 2H), 6.35 (s, 2H), 5.18 (s, 2H), 2.54 (t, J = 6.7 Hz, 4H), 2.22 (s, 4H), 1.99 - 1.90 (m, 4H), 1.31 (s, 10H).

Synthetic procedure of compound PLC-33 Compound PLC-33.1 General procedure for compound PLC-33.1 : PLC-32.1 (7.0 g, 16.50 mmol, 1 eq) was suspended in 2-MeTHF (150 mL), 4-(trifluoromethyl)phenylboronic acid (5.648 g , 29.7 mmol, 1.8 eq), K ₂ CO ₃ (4.65 g, 33 mmol, 2 eq), H ₂ O (15 ml), Pd(dppf)Cl ₂ DCM (269.5 mg, 0.33 mmol, 0.02 eq). Vac-Fill argon was circulated 3 times, the resulting mixture was stirred and heated at 95 °C under argon atmosphere for 12 hours, the mixture was cooled to room temperature, 1N HCl (20 ml) was added, stirred for 15 minutes, and then heated at RT. Leave on for 1 hour. The solid was filtered, stirred with DMF at room temperature for 15 minutes, then filtered, and the cyan-yellow solid was washed with MeOH and dried in a vacuum oven to give 6.70 g of a cyan-yellow solid, which was used in the next step without further purification . 83% yield. MS ₍ APCI): Calcd. for _C27H14F3NO5 (M-) _{= 489} ; found: 489. ¹ H NMR (400 MHz, DMSO-d ₆ ) δ 8.52 (s, 1H), 8.37 (q, J = 8.1, 7.7 Hz, 3H), 8.04 (d, J = 7.9 Hz, 2H), 7.93 (d, J = 8.7 Hz, 1H), 7.84 (d, J = 8.0 Hz, 2H), 7.49 (d, J = 8.6 Hz, 1H), 7.34 (d, J = 8.3 Hz, 1H), 4.67 (s, 2H) .

Compound PLC-33 General procedure for compound PLC- 33: PLC-33.1 (73.4 mg, 0.15 mmol, 1.5 eq) was suspended in anhydrous DCM (10.0 ml), PLC-2.1 (58.5 mg, 0.1 mmol, 1 eq) was added , DMAP-pTSA (58.8 mg, 0.2 mmol, 2 eq), EDC.HCl (57.5 mg, 0.3 mmol, 3 eq), stirred at room temperature under argon atmosphere for 5 hours, diluted with DCM (150 ml), Filtrate, wash the solid with 50 ml DCM, collect the filtrate, load onto _an 80 g SiO column, elute using Hex-DCM (1/1), DCM only, then DCM containing 0.5% EA, collect the pure fraction, Concentrated, washed with hot MeOH to afford 82 mg of a dark purple solid, 77% yield. MS _{( APCI} ) _: Calcd for Formula: _{C60H37BCl2F5N3O5} (M- ₎ = 1055; found _: 1055. ¹ H NMR (400 MHz, d ₂ -TCE) δ 8.66 (d, J = 7.9 Hz, 1H), 8.61 (d, J = 8.4 Hz, 1H), 8.21 (d, J = 2.2 Hz, 1H), 8.04 (d, J = 8.1 Hz, 1H), 7.96 (s, 2H), 7.73 (dd, J = 9.7, 1.8 Hz, H), 7.47 (d, J = 8.6 Hz, 1H), 7.38 (s, 1H) , 7.35 (d, J = 8.4 Hz, 1H), 7.27 (dt, J = 7.3, 3.7 Hz, 3H), 7.23 - 7.16 (m, 2H), 6.35 (s, 2H), 5.19 (s, 2H), 2.53 (d, J = 7.4 Hz, 4H), 2.22 (s, 4H), 2.03 - 1.86 (m, 4H).

Synthesis program of PLC-34 General procedure for compound PLC-34.1 : Ex-4.3 (1.223 g, 3.33 mmol, 1 eq) was suspended in 35 mL of anhydrous DMSO, and 5-amino-1-pentanol (0.687 g, 6.66 mmol, 2 eq) was added to the reaction mixture. The resulting mixture was stirred at 160 °C for 45 minutes, LMCMS showed the reaction was complete. After cooling to room temperature, the solid product was filtered, washed with water (250 mL) then MeOH (100 mL), and dried in a vacuum oven to give 1.2 g of a cyan solid, 85% yield. MS _{( APCI} ): Calcd. for _C23H18BrNO4 (M-) = 453; found: 453. ¹ H NMR (400 MHz, d ₂ -TCE) δ 8.52 (d, J = 7.8 Hz, 1H), 8.48 (d, J = 8.3 Hz, 1H), 8.09 (d, J = 2.3 Hz, 1H), 7.82 (d, J = 8.0 Hz, 1H), 7.54 (dd, J = 8.8, 2.3 Hz, 1H), 7.23 (d, J = 8.3 Hz, 1H), 7.19 (d, J = 8.8 Hz, 1H), 4.14 - 4.02 (m, 2H), 3.64 - 3.49 (m, 2H), 1.68 (p, J = 7.7 Hz, 2H), 1.60 - 1.54 (m, 2H), 1.41 (q, J = 8.0 Hz, 2H), 1.28 (s, 1H).

General procedure for compound PLC-34.2 : PLC-34.1 (1.13 g, 2.5 mmol, 1 eq) was suspended in DMF (10 ml), H ₂ O (5 ml), 4-trifluoromethylphenylboronic acid (0.949 g, 5.0 mmol, 2 eq), _K2CO3 (0.691 g, 5.0 mmol _, 2 eq), Pd(dppf)Cl2DCM ( _40.8 mg, 0.05 mmol, 0.02 eq). The mixture was degassed by Vac-Fill argon cycles 3 times, stirred and heated at 90°C for 5 hours. The reaction mixture was cooled to room temperature and water was added. The resulting mixture was kept at room temperature for 12 hours. The cyan-yellow solid was filtered, washed with water and then MeOH methanol to give 1.24 g of cyan-yellow solid, 95% yield. MS ₍ APCI): Calcd. for _C30H22F3NO4 (M-) _{= 517} ; found: 517. ¹ H NMR (400 MHz, d ₂ -TCE) δ 8.56 (d, J = 7.9 Hz, 1H), 8.51 (d, J = 8.3 Hz, 1H), 8.17 (d, J = 2.1 Hz, 1H), 7.97 (d, J = 8.0 Hz, 1H), 7.69 (dd, J = 10.3, 1.9 Hz, 4H), 7.42 (d, J = 8.6 Hz, 1H), 7.28 (d, J = 8.3 Hz, 1H), 4.09 (t, J = 7.5 Hz, 2H), 3.57 (q, J = 6.2 Hz, 2H), 1.69 (p, J = 7.8 Hz, 2H), 1.61 - 1.54 (m, 2H), 1.42 (q, J = 8.0 Hz, 2H), 1.28 (t, J = 5.5 Hz, 1H).

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 at 120° C. (HBr 48% bp: 126° C.) for 5 hours via a heating block , while stirring. After cooling to room temperature, the mixture was poured into ice water, 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 cyan-yellow solid was obtained with a yield of 93%. The product was used in the next step without further purification. MS ₍ APCI): Calcd. for _{C30H21BrF3NO3} (M-) = ₅₈₁ ; found _: 581. ¹ H NMR (400 MHz, d ₂ -TCE) δ 8.57 (d, J = 7.9Hz, 1H), 8.51 (d, J = 8.3 Hz, 1H), 8.18 (d, J = 2.2 Hz, 1H), 7.98 (d, J = 7.9 Hz, 1H), 7.69 (dd, J = 9.6, 2.0 Hz, 4H), 7.43 (d, J = 8.6 Hz, 1H), 7.28 (d, J = 8.3 Hz, 1H), 4.09 (t, J = 7.5 Hz, 3H), 3.38 (t, J = 6.7 Hz, 2H), 1.97 - 1.81 (m, 2H), 1.69 (t, J = 7.8 Hz, 2H).

Compound PLC-34 General procedure for compound PLC-34 : PLC-34.3 (87.06 mg, 0.15 mmol, 1.5 eq) was suspended in anhydrous DMF (10.0 ml), PLC-2.1 (63.65 mg, 0.10 mmol, 1 eq) was added , K ₂ CO ₃ (41.46 mg, 0.3 mmol, 2 eq), NaI (8.3 mg, catalytic amount). The resulting mixture was stirred at 65° C. under an argon atmosphere for 15 hours, cooled to room temperature, the solid was filtered, washed with 50 ml of water, and the crude product was loaded onto a 40 g silica gel column, and the mixture was collected using Hex:DCM (9: 1) to DCM dissolution, obtain 75 mg reddish-brown solid, productive rate 69%. MS (APCI) _{: Calcd} . _{for C63H45BCl2F5N3O4} (M-) = 1083; _{found :} 1083. ¹ H NMR (400 MHz, d ₂ -TCE) δ 8.59 (d, J = 7.9 Hz, 1H), 8.54 (d, J = 8.3 Hz, 1H), 8.18 (d, J = 2.1 Hz, 1H), 8.00 (d, J = 8.1 Hz, 1H), 7.96 (s, 1H), 7.70 (dd, J = 7.4, 2.2 Hz, 3H), 7.43 (d, J = 8.6 Hz, 1H), 7.30 (d, J = 8.3 Hz, 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 = 7.5 Hz, 2H), 3.99 (t, J = 6.2 Hz, 2H), 2.55 (t, J = 6.6 Hz, 2H), 2.23 (s, 2H), 1.98 - 1.92 (m, 2H), 1.86 (s, 1H), 1.77 (s , 1H), 1.58 (s, 2H).

Synthesis program of PLC-35 Compound PLC-35.1 – 9- Bromo -2-(2-(2- hydroxyethoxy ) ethyl )-1H- 𠮿 General procedure for [2,1,9-def]isoquinoline-1,3(2H)-dione : A 100 mL flask was fitted with a stir bar. Into the flask, Ex-4.3 (1.5 g, 4.1 mmol), 2-(2-aminoethoxy)ethan-1-ol (859.0 mg, 8.2 mmol) and DMAP (35.1 mg, 0.3 mmol) was degassed at room temperature. The reaction mixture was heated up to 165°C and the reaction was maintained at this temperature for 2 hours. TLC and LCMS showed the reaction was complete. The reaction was cooled to room temperature. _H2O (70 ml) was added to precipitate the product. The precipitate was collected by filtration. The solid was washed by _H2O (150 ml) and further dried in a vacuum oven at 100 °C for 3 hours to give PLC-35.1 as a yellow solid which was used in the next step without further purification. 1.45 g, 78% yield. MS ( _APCI ): Calcd. for _C22H16BrNO5 ([MH] ⁻ ) = ₄₅₄ Found: 454. ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) 8.62 (d, J = 8.0 Hz, 1H), 8.59 (d, J = 8.0 Hz, 1H), 8.19 (d, J = 2.4 Hz, 1H), 7.92 ( d, J = 8.0 Hz, 1H), 7.65 (dd, J = 8.0 Hz, J = 2.4 Hz, 2H), 7.33 (d, J = 8.0 Hz, 1H), 7.29 (d, J = 8.0 Hz, 1H) , 4.42 (t, J = 5.6 Hz, 2H), 3.85 (t, J = 5.6 Hz, 2H), 3.67 (m, 4H).

Compound PLC-35.2 – 2-(2-(2- hydroxyethoxy ) ethyl )-9-(4-( trifluoromethyl ) phenyl )-1H- 𠮿 General procedure for [2,1,9-def]isoquinoline-1,3(2H)-dione : A 250 mL flask was fitted with a stir bar. To the _flask , PLC-35.1 (800.0 mg, 1.8 mmol), 4-(trifluoromethyl)phenylboronic acid ( 670.0 mg, 3.5 mmol), Pd(dppf)Cl ₂ (90.6 mg, 0.1 mmol) and K ₂ CO ₃ (659.5 mg, 4.8 mmol) were degassed at room temperature. The reaction mixture was heated up to 80 °C and the reaction was kept at this temperature overnight. TLC was used to monitor the reaction. Upon completion, the reaction was worked up by addition of _H2O (150 ml) to precipitate the product. The precipitate was collected by filtration. The solid was washed by H ₂ O (200 ml) and MeOH (20 ml), and further dried in a vacuum oven at 100° C. for 3 hours to give PLC-35.2 as a yellow-green solid which was used in the next step without further purification. Quantitative yield. MS (APCI): _Calcd . for _C29H20F3NO5 ([M+H] ⁺ ) = ₅₂₀ Found _: 520. ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) 8.67 (d, J = 8.0 Hz, 1H), 8.61 (d, J = 8.0 Hz, 1H), 8.26 (d, J = 2.0 Hz, 1H), 8.07 ( d, J = 8.0 Hz, 1H), 7.79 (m, 5H), 7.52 (d, J = 8.4 Hz, 1H), 7.38 (d, J = 8.4 Hz, 1H), 5.11 (bs, 1H), 4.44 ( t, J = 1.6 Hz, 2H), 3.86 (t, J = 1.6 Hz, 2H), 3.68 (m, 4H).

Compounds PLC-35.3A and PLC-35.3B – Methanesulfonic acid 2-(2-(1,3- dioxo -9-(4-( trifluoromethyl ) phenyl )-1H- 𠮿 And [2,1,9-def] isoquinolin -2(3H)-yl ) ethoxy ) ethyl ester and 2-(2-(2- chloroethoxy ) ethyl )-9-(4- ( Trifluoromethyl ) phenyl )-1H- 𠮿 General procedure for [2,1,9-def]isoquinoline-1,3(2H)-dione : A 100 mL flask was fitted 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 up to 90°C and kept at this temperature for 20 minutes. TLC was used to monitor the reaction. Upon completion, the reaction was worked up by addition of _H2O (150 ml) to precipitate the product. The precipitate was collected by filtration. The solid was washed by H ₂ O (100 ml) and MeOH (15 ml), and further dried in a vacuum oven at 100° C. for 3 hours to give PLC-35.3A and PLC-35.3B as yellow solids (ca. 1:1 molar ratio) was used in the next step without further purification. Quantitative yield. For PLC-35.4A, MS (APCI): Calculated for C ₃₀ H ₂₂ F ₃ NO ₇ S ([M+H] ⁺ ) = 598 Found: 598. ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) 8.65 (d, J = 8.0 Hz, 1H), 8.60 (d, J = 8.0 Hz, 1H), 8.26 (d, J = 2.0 Hz, 1H), 8.07 ( d, J = 8.0 Hz, 1H), 7.78 (m, 5H), 7.52 (d, J = 8.4 Hz, 1H), 7.38 (d, J = 8.4 Hz, 1H), 4.44 (t, J = 2.0 Hz, 2H), 4.35 (m, 2H), 3.86 (t, J = 2.0 Hz, 2H), 3.81 (m, 2H), 3.01 (s, 3H). For PLC _{-35.4B, MS (APCI): Calcd. for C29H19CIF3NO4 ( [} MH] ^- ) = 537 Found: ₅₃₇ . ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) 8.66 (d, J = 8.0 Hz, 1H), 8.61 (d, J = 8.0 Hz, 1H), 8.26 (d, J = 2.0 Hz, 1H), 8.07 ( d, J = 8.0 Hz, 1H), 7.79 (m, 5H), 7.52 (d, J = 8.4 Hz, 1H), 7.37 (d, J = 8.4 Hz, 1H), 4.43 (t, J = 2.0 Hz, 2H), 3.86 (t, J = 2.0 Hz, 2H), 3.81 (t, J = 1.6 Hz, 2H), 3.63 (t, J = 1.6 Hz, 2H).

Compound PLC-35.4 – 2,6- dichloro -4-(2-(2-(1,3- dioxo -9-(4-( trifluoromethyl ) phenyl )-1H- 𠮿 General procedure for [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 kept stirring 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 up to 160 °C and kept stirring at this temperature overnight. TLC (50% EtOAc in hexanes) showed the reaction was complete. The reaction mixture was purified by flash chromatography on silica gel using EtOAc in DCM (0 to 40%) as eluent to give pure compound PLC-35.4 as a yellow solid, 580.0 mg, 60% yield. MS _{( APCI} ): _Calcd . for _{C36H22Cl2F3NO6} ([MH] ^- ) = ₆₉₁ Found: 691. ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) δ 10.06 (s, 1H), 8.60 (d, J = 8.0 Hz, 1H), 8.57 (d, J = 8.0 Hz, 1H), 8.24 (d, J = 2.0 Hz, 1H), 8.02 (d, J = 8.0 Hz, 1H), 7.81 (m, 5H), 7.52 (d, J = 8.0 Hz, 1H), 7.34 (d, J = 8.0 Hz, 1H), 6.56 (s, 2H), 4.44 (t, J = 2.0 Hz, 2H), 3.98 (m, 2H), 3.93 (t, J = 2.0 Hz, 2H), 3.86 (m, 2H).

Compound PLC-35 – 2-(2-(2-(3,5- dichloro -4-(19,19- difluoro -6,7,11,12,13,19- hexahydro -5H-18l4, 19l4- 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- 𠮿 General procedure for [2,1,9-def]isoquinoline-1,3(2H)-dione : A 100 mL 2-neck round bottom flask was equipped with an air condenser and a stirring bar. To the flask was 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 min, then p-TsOH•H ₂ O (1.2 mg, 0.01 mmol) was added. The reaction solution was kept at this temperature for 2 hours. Then DDQ (25.0 mg, 0.1 mmol) was added. The reaction was kept at room temperature for 30 minutes. Then BF ₃ •OEt ₂ (0.3 mL, 2.4 mmol) and Et ₃ N (0.2 mL, 1.6 mmol) were added at room temperature. The reaction mixture was kept at room temperature overnight. The reaction mixture was loaded on silica gel and purified by flash chromatography using EtOAc in DCM (0 to 5%) as eluent to give pure PLC-35 as a dark purple solid, 121.0 mg, 55% yield. MS _{( APCI ): Calcd. for C62H43BCl2F5N3O5 ( [} MH] ^- ) = 1086 Found _: 1086. ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) 8.69 (d, J = 8.0 Hz, 1H), 8.63 (d, J = 8.0 Hz, 1H), 8.26 (d, J = 2.4 Hz, 1H), 8.08 ( d, J = 8.0 Hz, 1H), 8.04 (m, 2H), 7.78 (m, 5H), 7.51 (d, J = 8.0 Hz, 1H), 7.34 (m, 7H), 6.99 (s, 2H), 6.44 (s, 2H), 4.49 (t, J = 2.0 Hz, 2H), 4.18 (m, 2H), 3.96 (m, 4H), 2.63 (m, 4H), 2.31 (bs, 4H), 2.04 (m , 4H).

Synthetic procedure of compound PLC-36 Compound PLC-36.5– (2-(4-(9- bromo -1,3- dioxo -1H- 𠮿 General procedure for [ 2,1,9-def] isoquinolin -2(3H)-yl )phenyl ) acetic acid ) : A 100 mL 2N round bottom flask was placed in an aluminum heating block and a stir bar was placed. The flask was fitted with a finned condenser/gas adapter and 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 heating block was set to 170 °C. The reaction mixture was stirred at 170°C for 9 hours and then at room temperature. The crude reaction mixture was diluted with 75 mL of water. The mixture was stirred for 5 minutes, then the crude product was filtered off and dried by suction for 5 minutes. The wet precipitate was dried overnight in a vacuum oven at about 110°C. A yellowish powder was obtained, 366 mg (107% yield). NMR showed about 10 to 15% dimethylamide by-product. MS ( _APCI ) _: Calcd. for _C26H14BrNO5 (M+H) = 500; found: 500. ¹ H NMR (400 MHz, DMSO- d ₆ ) δ 8.60 (d, J = 2.3 Hz, 1H), 8.49 - 8.45 (m, 2H), 8.39 (d, J = 8.1 Hz, 1H), 7.80 - 7.75 ( m, 1H), 7.48 - 7.43 (m, 2H), 7.43 - 7.38 (m, 2H), 7.31 - 7.27 (m, 2H), 3.67 (s, 2H).

Compound PLC-36.2 – (2-(4-(2-(2-(2- methoxyethoxy ) ethoxy ) ethoxy ) phenyl )-4,4,5,5 - tetramethyl- General procedure for 1,3,2- dioxaborolane ) : Place a 250 mL 2N round bottom flask in an aluminum heating block and place a stir bar. The flask was fitted with a finned condenser/gas adapter and 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 _K2CO3 ( _11.0 mmol, 1.520 g). The reaction mixture was stirred at room temperature under an atmosphere of argon for 5 minutes, then the heat block was set at 50°C and the reaction mixture was stirred at 50°C for 6 hours, then at room temperature over the weekend. The reaction mixture was diluted with water (about 200 mL), then extracted with diethyl ether (3 X 100 mL). The combined ether layers were washed with saturated aqueous NaHCO ₃ (50 mL), brine (50 mL), dried over MgSO ₄ , filtered and evaporated to dryness in vacuo. A pale yellow oil was obtained (4.166 g, 114% yield). NMR indicated it was a mixture of desired product and starting bromo-glycol, estimated about 57% product. Used in the next step without further purification. MS (APCI): calcd for _C19H31BO6 (M+H) = 367; found _{: 367} . ¹ H NMR (400 MHz, methanol- d ₄ ) δ 7.69 - 7.63 (m, 2H), 6.95 - 6.90 (m, 2H), 4.18 - 4.11 (m, 2H), 3.86 - 3.82 (m, 2H), 3.72 - 3.67 (m, 2H), 3.66 - 3.60 (m, 2H), 3.54 - 3.48 (m, 4H), 3.34 (s, 3H).

Compound PLC-36.3 – (2-(4-(9-(4-(2-(2-(2- methoxyethoxy ) ethoxy ) ethoxy ) phenyl )-1,3- two sides Oxy -1H- 𠮿 General procedure for [ 2,1,9-def] isoquinolin -2(3H) -yl ) phenyl ) acetic acid ) : A 250 mL 2N round bottom flask was placed in an aluminum heating block and a stir bar was placed. The flask was fitted with a finned condenser/gas adapter and flow control valve. The system was flushed with argon. To the flask was added PLC-36.1 (2.00 mmol, 1001 mg), PLC-36.2 (4.00 mmol, 1465 mg), K ₂ CO ₃ (5.50 mmol, 760 mg) and Pd(dppf)Cl ₂ (0.140 mmol, 102 mg), followed by the addition of 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 was continued under argon. Set the heat block at 80 °C for 2 hours. The reaction mixture was quenched with 6N HCl (5 mL) and diluted with water (50 mL) and THF (50 mL). Sodium chloride was added until the aqueous layer was saturated, then the layers were separated, and the aqueous layer was extracted with THF (3×50 mL). The combined organic layers were washed with brine (50 mL), dried over MgSO ₄ , filtered, and evaporated to dryness (containing DMF) in vacuo. The crude product was evaporated onto about 50 g of flash silica gel and placed in a loader. Purified by flash chromatography on silica gel (220 g, solid load, equilibrated 100% DCM, eluting 100% DCM (2 CV) à 40% (EtOAc/0.1% TFA)/DCM (20CV) à 70% (EtOAc /0.1% TFA)/DCM (20 CV)). Fractions containing product were evaporated to dryness in vacuo. Obtained a yellow solid, 722 mg (55% yield). MS (APCI): Calcd. for _C39H33NO9 (M+H) = 660; found _{: 660} . ¹ H NMR (400 MHz, DMSO- d ₆ ) δ 8.57 (d, J = 2.2 Hz, 1H), 8.52 (s, 2H), 8.48 (d, J = 8.3 Hz, 1H), 7.90 (dd, J = 8.7, 2.2 Hz, 1H), 7.84 - 7.78 (m, 2H), 7.55 (d, J = 8.7 Hz, 1H), 7.48 (d, J = 8.3 Hz, 1H), 7.41 (d, J = 8.1 Hz, 2H), 7.33 - 7.26 (m, 2H), 7.12 - 7.07 (m, 2H), 4.22 - 4.14 (m, 2H), 3.82 - 3.76 (m, 2H), 3.68 (s, 2H), 3.65 - 3.59 ( m, 2H), 3.58 - 3.51 (m, 4H), 3.48 - 3.41 (m, 2H), 3.25 (s, 3H).

Compound PLC-36 – 2-(4-(9-(4-(2-(2-(2- methoxyethoxy ) ethoxy ) ethoxy ) phenyl )-1,3- dioxo base -1H- 𠮿 And [2,1,9-def] isoquinolin -2(3H)-yl ) phenyl ) acetic acid (3,5- dichloro -4-(19,19 -difluoro -6,7,11,12 ,13,19- Hexahydro -5H-18l4,19l4- 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 ester ) general procedure : Add a stir bar to a 40 mL vial, followed by PLC-2.1 – 3,5-dichloro-4-(19,19-difluoro-6,7,11,12,13,19-hexahydro-5H- 18l4,19l4-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.p TsOH 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 overnight at room temperature. The crude reaction was quenched with a few drops of TFA and loaded onto approximately 65 g of flash silica gel in a loader. Purified by flash chromatography on silica gel (120 g, solids load, equilibrated 100% DCM, eluted 100% DCM (3 CV) à 5.8% EtOAc/DCM (11.6 CV) à 13.3% EtOAc/DCM (6.0 CV) à 50% EtOAc/DCM (10 CV). Fractions containing product were evaporated to dryness in vacuo. The crude product was triturated with hot methanol. The product was filtered off, dried by suction and then dried in a vacuum oven at about 110°C. Obtained as a dark red solid, 47.1 mg (77% yield). MS ₍ APCI) _: Calcd. _{for C72H56BCl2F2N3O9} (M-) = ₁₂₂₅ ; _found : 1225. ¹ H NMR (400 MHz, tetrachloroethane - d ₂ ) δ 8.68 (d, J = 7.8 Hz, 1H), 8.63 (d, J = 8.3 Hz, 1H), 8.25 (d, J = 2.1 Hz, 1H ), 8.11 (d, J = 8.1 Hz, 1H), 8.09 - 8.00 (m, 2H), 7.78 (dd, J = 8.6, 2.1 Hz, 1H), 7.69 - 7.61 (m, 4H), 7.50 (d, J = 8.6 Hz, 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 = 4.7 Hz , 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 = 6.8 Hz, 4H), 2.44 - 2.22 (m, 4H), 2.12 - 1.97 (m, 4H).

Synthetic procedure of compound PLC-37 Compound PLC-37.1 – (9- bromo -2-(2- hydroxyethyl )-1H- 𠮿 General procedure for [ 2,1,9-def] isoquinoline -1,3(2H) -dione ) : Place a 50 mL 2N round bottom flask in an aluminum heating block and place a stir bar. The flask was fitted with a finned condenser/gas adapter, stopper and flow control valve. The system was flushed with argon. To the flask was added 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 heating block was set to 165°C. The reaction mixture was stirred at this temperature for 3 hours, then the reaction mixture was cooled to room temperature. The solvent was evaporated to dryness in vacuo. The residue was triturated with water (50 mL) and 6N aqueous HCL (10 mL). The mixture was sonicated for several minutes, then stirred at room temperature for 30 minutes, then the solid product was filtered off and washed with water. The crude filter cake was dried overnight in a vacuum oven at about 110°C. Obtained as a dark brown solid, 1.038 g (84% yield). MS ( _APCI ): Calcd. for _C20H12BrNO4 (M+H) = 410; found: 410 _.

Compound PLC-37.2 – (2-(2- Hydroxyethyl )-9-(4-( trifluoromethyl ) phenyl )-1H- 𠮿 General procedure for [ 2,1,9-def] isoquinoline -1,3(2H) -dione ) : PLC- 39.2 is self-contained in THF/DMF/H ₂ O ( 60 mL/12 mL/6 mL) of PLC-37.1 (2.531 mmol, 1.038 g), (4-(trifluoromethyl)phenyl)boronic acid (5.062 mmol, 961 mg), K ₂ CO ₃ (6.960 mmol , 962 mg) and Pd(dppf)Cl ₂ (0.177 mmol, 130 mg) were synthesized at 80°C for 30 minutes. The crude product was precipitated by adding water (100 mL), then the resulting solid was filtered off and washed with water. The crude product was triturated with methanol, then dried in a vacuum oven at about 110 °C overnight. Obtained 1.017 g (84% yield). MS (APCI): Calcd. for _C27H16F3NO4 (M+H) _{= 476} ; found _: 476. ¹ H NMR (400 MHz, TCE) δ 8.66 (d, J = 7.8 Hz, 1H), 8.61 (d, J = 8.3 Hz, 1H), 8.25 (d, J = 2.2 Hz, 1H), 8.06 (d, J = 8.0 Hz, 1H), 7.83 - 7.75 (m, 5H), 7.52 (d, J = 8.6 Hz, 1H), 7.37 (d, J = 8.4 Hz, 1H), 4.45 (t, J = 5.2 Hz, 2H), 3.98 (q, J = 5.3 Hz, 2H), 2.49 (t, J = 5.5 Hz, 1H).

Compound PLC-37.3 – (2-(2- Chloroethyl )-9-(4-( trifluoromethyl ) phenyl )-1H- 𠮿 General procedure for [ 2,1,9-def] isoquinoline -1,3(2H) -dione ) : Place a 250 mL 2N round bottom flask in an aluminum heating block and place a stir bar. The flask was fitted with a finned condenser/gas adapter, stopper and flow control valve. The system was flushed with argon. To the flask was added PLC-37.2 (2.124 mmol, 1.01 g), pTsCl (6.372 mmol, 1.215 g), anhydrous DMF (20 mL) and _Et3N (6.372 mmol, 0.888 mL). The reaction mixture was stirred and heated to 80 °C under argon for 2 hours. When the tosylate was displaced in situ by the chloride ion, an unexpected reaction occurred. 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. Obtained 974 mg of an orange solid (93% yield). MS (APCI): calcd for _{C27H15ClF3NO3} (M+H) = ₄₉₄ ; found _{: 494} . ¹ H NMR (400 MHz, TCE) δ 8.67 (d, J = 7.9 Hz, 1H), 8.62 (d, J = 8.3 Hz, 1H), 8.27 (d, J = 2.2 Hz, 1H), 8.08 (d, J = 7.9 Hz, 1H), 7.86 - 7.73 (m, 5H), 7.53 (d, J = 8.6 Hz, 1H), 7.39 (d, J = 8.4 Hz, 1H), 4.56 (t, J = 6.9 Hz, 2H), 3.87 (t, J = 6.8 Hz, 2H).

Compound PLC-37.4 – (2,6- dichloro -4-(2-(1,3- dioxo -9-(4-( trifluoromethyl ) phenyl )-1H- 𠮿 General procedure for [ 2,1,9-def] isoquinolin -1,3(2H) -yl ) ethoxy ) benzaldehyde ) : Place a 100 mL 2N round bottom flask in an aluminum heating block and place stir bar. The flask was fitted with a finned condenser/gas adapter, stopper and flow control valve. The system was flushed with argon. To the flask was added NaH (60% in mineral oil) (1.214 mmol, 29.1 mg, 60%, 49 mg) followed by dry 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 heating block was set at 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. Increase the heating block temperature to 160°C. The reaction mixture was stirred at 160°C for 90 minutes, then at room temperature overnight. The crude product was precipitated by adding water (100 mL) and filtering off the product, washing with water. The crude product was dissolved in DCM and evaporated to dryness in vacuo. The crude product was evaporated in vacuo onto a flash of silica gel (ca. 20 g). Purified by flash chromatography on silica gel (120 g, solids load, equilibrated 100% DCM/hexane, eluting 100% DCM/hexane (7 CV) à 0% EtOAc/DCM (0 CV) à 0% EtOAc /DCM (5 CV) à 40% EtOAc/DCM (40 CV). Fractions containing product were evaporated to dryness in vacuo. 152 mg (39% yield) of a yellow solid was obtained. MS (APCI): for C ₃₄ Calcd ^for H ₁₈ Cl ₂ F ₃ NO ₅ (M-) = 647; , 8.63 (d, J = 8.3 Hz, 1H), 8.26 (d, J = 2.1 Hz, 1H), 8.07 (d, J = 8.0 Hz, 1H), 7.85 - 7.72 (m, 5H), 7.52 (d, J = 8.6 Hz, 1H), 7.39 (d, J = 8.4 Hz, 1H), 6.99 (s, 2H), 6.93 (s, 1H), 4.65 (t, J = 6.1 Hz, 2H), 4.40 (t, J = 6.1 Hz, 2H).

Compound PLC-37 Compound PLC-37 – (2-(2-(3,5- dichloro -4-(19,19- difluoro -6,7,11,12,13,19- hexahydro -5H- 18l4,19l4- 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-( trifluoro Methyl ) phenyl )-1H- 𠮿 General procedure for [ 2,1,9-def] isoquinoline -1,3(2H) -dione ) : Place a 100 mL 2N round bottom flask in an aluminum heating block and place a stir bar. The flask was fitted with a finned condenser/gas adapter, stopper and flow control valve. The system was flushed with argon. To this flask was added 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), followed by the addition of anhydrous DCM (20 mL). Under an atmosphere of argon, the reaction mixture was sparged with nitrogen for 10 minutes. A pair of small particles of pTsOH.H2O aggregated at the end of _the spatula and dipped these into the reaction mixture. Stirring was continued and sparged with nitrogen for another 5 minutes. The nitrogen sparge was stopped and the reaction mixture was stirred at room temperature for 1 hour, at which time TLC showed 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 indicated complete oxidation to dipyrromethane. To the flask was added Et ₃ N (0.600 mmol, 0.084 mL) and BF ₃ .OEt ₂ (0.900 mmol, 0.111 mL). The addition of both reagents was repeated after 2 minutes, then the heat block was set to 50°C and the reaction mixture was stirred at this temperature under argon for 2 hours. Crude BODIPY was loaded directly onto flash silica gel (25 g). Purify by flash chromatography on silica gel (80 g, solids load, equilibrate 80% DCM/hexane, elute 80% DCM/hexane (2 CV) à 100 DCM/hexane (5 CV) à isocratic 100 % DCM/hexane (about 25 CV) à 100% DCM/hexane/0.5% EtOAc modifier (about 10 CV)). The product elutes as a broad peak. Fractions containing product were evaporated to dryness in vacuo. Obtained as a dark red solid, 89 mg (quantitative yield). MS (APCI) _{: Calcd. for C60H39BCl2F5N3O4 ( M- )} = 1041; _found 1041. ¹ H NMR (400 MHz, TCE) δ 8.72 (d, J = 7.9 Hz, 1H), 8.67 (d, J = 8.4 Hz, 1H), 8.27 (d, J = 2.2 Hz, 1H), 8.10 (d, J = 8.1 Hz, 1H), 8.04 (dd, J = 5.8, 3.5 Hz, 2H), 7.84 - 7.75 (m, 5H), 7.53 (d, J = 8.6 Hz, 1H), 7.41 (d, J = 8.3 Hz, 1H), 7.39 - 7.32 (m, 4H), 7.32 - 7.25 (m, 2H), 7.14 (s, 2H), 4.70 (t, J = 6.2 Hz, 2H), 4.42 (t, J = 6.2 Hz , 2H), 2.62 (t, J = 7.0 Hz, 4H), 2.41 - 2.18 (m, 4H), 2.11 - 1.93 (m, 4H).

Synthesis program of PLC-38 Synthesis of PLC-38.1 (9- bromo -2-(3- hydroxypropyl )-1H- 𠮿 and [2,1,9-def] isoquinoline -1,3(2H) -dione ) : Suspend Ex-4.3 (1.223 g, 3.33 mmol, 1 eq) in 35 mL of anhydrous DMSO at RT , 3-Amino-1-propanol (1.5 g, 20.0 mmol, 6 eq) was added to the reaction mixture. The resulting mixture was stirred at 160 °C for 45 minutes, LCMS showed the reaction was complete. After cooling to room temperature, the solid product was filtered, the solid was washed with water (250 mL) then MeOH (100 mL), and dried in a vacuum oven to give 1.2 g of a cyan-yellow solid in 92% yield. MS ( _APCI ): Calcd. for _C23H18BrNO4 (M-) ₌ 425; found: 425. ¹ H NMR (400 MHz) δ 8.56 (d, J = 7.9 Hz, 1H), 8.52 (d, J = 8.4 Hz, 1H), 8.13 (d, J = 2.3 Hz, 1H), 7.86 (d, J = 7.9 Hz, 1H), 7.57 (dd, J = 8.8, 2.3 Hz, 1H), 7.26 (d, J = 8.4 Hz, 1H), 7.22 (d, J = 8.8 Hz, 1H), 4.24 (t, J = 6.1 Hz, 2H), 3.48 (q, J = 6.1 Hz, 2H), 3.06 (t, J = 6.9 Hz, 1H), 1.95 - 1.83 (m, 2H).

Synthesis of PLC-38.2 (2-(3- hydroxypropyl )-9-(4-( trifluoromethyl ) phenyl )-1H- 𠮿 and [2,1,9-def] isoquinoline -1,3(2H) -dione ) : PLC-38.1 (1.06 g, 2.5 mmol, 1 eq) was suspended in DMF (10 ml), H ₂ O (5 ml), add 4-trifluoromethylphenylboronic acid (0.949 g, 5.0 mmol, 2 eq), K ₂ CO ₃ (0.691 g, 5.0 mmol, 2 eq), Pd(dppf)Cl ₂ ·DCM ( 40.8 mg, 0.05 mmol, 0.02 eq). The mixture was degassed by Vac-Fill argon cycles 3 times, stirred and heated at 90°C for 5 hours. The reaction mixture was cooled to room temperature and water was added. The resulting mixture was kept at room temperature for 12 hours. The cyan solid was filtered, washed with water and then MeOH to give 1.04 g of cyan solid, 85% yield. MS ₍ APCI): Calcd. for _C30H22F3NO4 (M-) = _{517 ;} found: 517. ¹ H NMR (400 MHz) δ 8.56 (d, J = 7.9 Hz, 1H), 8.51 (d, J = 8.3 Hz, 1H), 8.17 (d, J = 2.1 Hz, 1H), 7.97 (d, J = 8.0 Hz, 1H), 7.69 (dd, J = 10.3, 1.9 Hz, 4H), 7.42 (d, J = 8.6 Hz, 1H), 7.28 (d, J = 8.3 Hz, 1H), 4.09 (t, J = 7.5 Hz, 2H), 3.57 (q, J = 6.2 Hz, 2H), 1.69 (p, J = 7.8 Hz, 2H), 1.61 - 1.54 (m, 2H), 1.42 (q, J = 8.0 Hz, 2H) , 1.28 (t, J = 5.5 Hz, 1H).

Synthesis of PLC-38.3 (2-(3- bromopropyl )-9-(4-( trifluoromethyl ) phenyl )-1H- 𠮿 And [2,1,9-def] isoquinoline -1,3(2H) -dione ) : A mixture of PLC-38.2 (1.6 g, 3.2 mmol) and 48% HBr aqueous solution (30.0 ml) was heated by The mass was heated to reflux at 130°C for 3 days with stirring. The same volume of 48% aq HBr was added more than 2 times over the next 2 days, for a total of 90 ml. After cooling to room temperature, the mixture was poured into ice water, 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 cyan-yellow solid was obtained with a yield of 96%. The product was used in the next step without further purification. MS ₍ APCI): Calcd. for _{C30H21BrF3NO3} (M-) = ₅₅₁ ; found _: 551. ¹ H NMR (400 MHz) δ 8.55 (d, J = 7.9 Hz, 1H), 8.50 (d, J = 8.4 Hz, 1H), 8.15 (d, J = 2.2 Hz, 1H), 7.96 (d, J = 8.0 Hz, 1H), 7.70 (s, 5H), 7.41 (d, J = 8.6 Hz, 1H), 7.27 (d, J = 8.3 Hz, 1H), 4.22 (t, J = 7.1 Hz, 2H), 3.45 (t, J = 6.8 Hz, 2H), 2.25 (q, J = 6.9 Hz, 2H).

Synthesis of PLC-38 (2-(3-(3,5- dichloro -4-(19,19- difluoro -6,7,11,12,13,19- hexahydro -5H-18l4,19l4- benzene And [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] biheteroborin-9-yl)phenoxy ) propyl ) -9- ( 4- ( trifluoromethyl ) phenyl )- 1H- 𠮿 and [2,1,9-def] isoquinoline -1,3(2H) -dione ) : PLC-38.3 (41.425 mg, 0.075 mmol, 1.15 eq) was suspended in anhydrous DMF (2.0 ml), added PLC-2.1 (38.04 mg, 0.065 mmol, 1 eq), _K2CO3 (0.73 mg, 0.15 mmol, 2.3 eq), _NaI (4.15 mg). The resulting mixture was stirred at 85° C. under an argon atmosphere for 16 hours, cooled to room temperature, the solid was filtered, washed with 50 ml of water, and the crude product was loaded onto a 40 g silica gel column, and the mixture was collected using Hex:DCM (9: 1) to DCM dissolution, to obtain 49 mg dark purple solid, yield 71%. MS ₍ APCI) _{: Calcd} . _{for C63H45BCl2F5N3O4} (M-) = ₁₀₅₅ ; found: 1055. ¹ H NMR (400 MHz, ) δ 8.60 (d, J = 7.8 Hz, 1H), 8.55 (d, J = 8.3 Hz, 1H), 8.18 (d, J = 2.2 Hz, 1H), 8.00 (d, J = 8.1 Hz, 1H), 7.95 (d, J = 5.9 Hz, 2H), 7.74 - 7.65 (m, 4H), 7.44 (d, J = 8.6 Hz, 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 = 6.9 Hz, 2H), 4.13 (t, J = 6.1 Hz, 2H), 2.54 (t, J = 6.7 Hz, 4H), 2.28 - 2.19 (m, 4H), 2.06 - 1.85 (m, 4H), 0.78 (d, J = 14.2 Hz, 2H).

Synthesis program of PLC-39 Compound 39.1 : Compound Ex-4.4 (649 mg, 1.23 mmol), 4-(trifluoromethyl)phenylboronic acid ( A mixture of 467 mg, 2.46 mmol), Pd(dppf) _Cl2 (45 mg, 0.06 mmol), potassium carbonate (345 mg, 2.5 mmol) was degassed and then heated at 80°C overnight. The mixture was treated with 300 mL ethyl acetate and 50 mL 0.6 N aqueous hydrochloric acid. The aqueous phase was extracted with ethyl acetate (150 mL x 3). The organic phase was collected and washed with brine (100 mL x 2), dried over sodium sulfate, then dry-loaded on silica gel and eluent by flash chromatography using DCM/EA (0% to 80% EA and 0.1% TFA) purification. The main desired fractions were collected and the solvent was removed under reduced pressure to give a yellow solid (414 mg, 57% yield). ¹ H NMR (400 MHz, d ₂ -TCE) δ 8.55 (dd, J = 18.1, 8.1 Hz, 2H), 8.16 (d, J = 2.2 Hz, 1H), 8.00 (d, J = 8.1 Hz, 1H) , 7.68 (dd, J = 8.6, 2.1 Hz, 1H), 7.66 - 7.59 (m, 2H), 7.43 (d, J = 8.6 Hz, 1H), 7.32 (tt, J = 8.2, 4.2 Hz, 5H), 7.20 - 7.13 (m, 2H), 2.72 (t, J = 7.6 Hz, 2H), 2.39 (t, J = 7.3 Hz, 2H), 1.99 (q, J = 7.4 Hz, 2H).

Compound PLC-39 : 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/ A mixture of p-TsOH (15 mg, 0.05 mmol) 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 10% ethyl acetate). The main red fractions were collected and concentrated under reduced pressure to 0.5 mL, then 10 mL of methanol was added. The resulting precipitate was filtered and air dried to give a dark red solid (44 mg, 69% yield). ¹ H NMR (400 MHz, d ₂ -TCE) δ 8.56 (dd, J = 17.8, 8.1 Hz, 2H), 8.16 (d, J = 2.2 Hz, 1H), 7.99 (dd, J = 19.8, 6.8 Hz, 3H), 7.68 (dd, J = 8.6, 2.1 Hz, 1H), 7.66 - 7.59 (m, 2H), 7.44 (d, J = 8.6 Hz, 1H), 7.41 - 7.35 (m, 2H), 7.35 - 7.25 (m, 9H), 7.22 (dd, J = 8.7, 4.2 Hz, 4H), 6.40 (s, 2H), 2.82 (t, J = 7.5 Hz, 2H), 2.67 (t, J = 7.4 Hz, 2H) , 2.55 (t, J = 6.7 Hz, 4H), 2.24 (bs, 4H), 2.14 (q, J = 7.5 Hz, 2H), 1.96 (t, J = 7.1 Hz, 4H).

Synthesis program of PLC-40 Compound 40.1 : 9-bromo-2-(3-hydroxypropyl)-1H-𠮿 in 1,4-dioxane/DMF/water (15 mL/3 mL/1.5 mL) A[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(PPh ₃ ) ₄ (80 mg, 0.069 mmol), K ₂ CO ₃ (320 mg, 2.32 mmol) was degassed and heated at 90° C. for 24 hours. The resulting mixture was treated with water and ethyl acetate. The organic phase was collected and loaded on silica gel, purified by flash chromatography using the eluent of DCM/EA (0% to 40% EA). The desired fractions were collected and a yellow solid (210 mg, 49% yield) was obtained after removal of the solvent under reduced pressure. LCMS (APCI-): Calcd. for _{C36H37NO4 , 547.27} ; found: 547. ¹ H NMR (400 MHz, d ₂ -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 = 6.1 Hz, 2H), 4.01 (q, J = 7.2 Hz, 2H), 3.47 (t, J = 5.5 Hz, 2H), 2.88 (p, J = 6.8 Hz, 1H), 2.65 - 2.43 (m , 2H), 1.89 (d, J = 6.2 Hz, 2H), 1.24 (d, J = 6.9 Hz, 6H), 1.03 (t, J = 7.1 Hz, 12H).

Compound 40.2 : To a solution of compound PLC-40.1 (210 mg, 0.384 mmol) in 20 mL of DCM was added carbon tetrabromide ( _CBr4 , 252 mg, 0.76 mmol), triphenylphosphine at room temperature (203 mg, 0.77 mmol). The whole was stirred for 30 minutes. TLC showed the reaction was complete. The mixture was loaded on silica gel and purified by flash chromatography using the 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+): Calcd. for _C36H37BrNO3 (M+H): _610.19 ; found: ₆₁₀ . ¹ H NMR (400 MHz, d ₂ -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).

Compound 40 : A mixture of compounds PLC-40.2 (50 mg, 0.082 mmol), PLC-1.3 (58.5 mg, 0.10 mmol), K ₂ CO ₃ (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 h. The resulting mixture was diluted with 100 mL of DCM, washed with 0.1 N aqueous HCl (50 mL x 2), dried over MgSO ₄ , concentrated to 50 mL, then loaded onto silica gel, and purified by flash chromatography using DCM/EA ( 0% to 5% EA) for eluent purification. The main desired fractions were collected, concentrated and triturated with methanol followed by filtration to give a dark red solid (70 mg, 76.6% yield). _{LCMS (} APCI-): _Calcd . _{for C69H60BCl2F2N3O4} : _1113.40 ; found: 1113. ¹ H NMR (400 MHz, d ₂ -TCE) δ 8.63 - 8.43 (m, 2H), 8.08 - 7.72 (m, 4H), 7.46 - 7.13 (m, 9H), 6.94 (d, J = 31.3 Hz, 4H ), 6.38 (s, 2H), 4.35 (t, J = 6.8 Hz, 2H), 4.12 (t, J = 5.9 Hz, 2H), 2.98 - 2.77 (m, 1H), 2.54 (q, J = 6.8 Hz , 6H), 2.23 (d, J = 6.0 Hz, 6H), 2.04 - 1.89 (m, 4H), 1.23 (d, J = 6.9 Hz, 6H), 1.02 (dd, J = 6.9, 3.5 Hz, 12H) .

Synthesis of compound PLC-41 General procedure for the synthesis of compound PLC-41.1 — 9-bromo-2-(4-hydroxybutyl)-1H-𠮿 And[2,1,9-def]isoquinoline-1,3(2H)-dione: Install a 100 mL flask with a stir bar. Into the flask, 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) was degassed at room temperature. The reaction mixture was heated up to 165°C and the reaction was maintained at this temperature for 2.5 hours. TLC and LCMS showed the reaction was complete. The reaction was cooled to room temperature. _H2O (80 ml) was added. The solid product was collected by vacuum filtration and washed with _H2O (100 ml) and further dried in a vacuum oven at 100 °C for 3 hours to give PLC-41.1 as a brown solid which was used in the next step without further purification. 908.0 mg, 77% yield. MS (APCI): Calcd for Formula _C22H16BrNO4 ([MH]-) = ₄₃₈ Found: ₄₃₈ . ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) 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).

General procedure for the synthesis of compound PLC-41.2 — 2-(4-hydroxybutyl)-9-(4-(trifluoromethyl)phenyl)-1H-𠮿 And[2,1,9-def]isoquinoline-1,3(2H)-dione: A 250 mL flask was fitted with a stir bar. To the flask, compound PLC-41.1 (900.0 mg, 2.1 mmol), 4-(trifluoromethyl)phenylboronic acid in THF/DMF/H ₂ O (60 ml/ 12 ml/ 6 ml) (780.0 mg, 4.1 mmol), Pd(dppf)Cl ₂ (107.5 mg, 0.15 mmol) and K ₂ CO ₃ (782.5 mg, 5.7 mmol) were degassed at room temperature. The reaction mixture was heated up to 80 °C and the reaction was kept at this temperature overnight. TLC was used to monitor the reaction. Upon completion, the reaction was worked up by addition of _H2O (150 ml) to precipitate the product. The precipitate was collected by filtration. The solid was washed by H ₂ O (200 ml) and MeOH (20 ml), and further dried in a vacuum oven at 100° C. for 3 hours to give PLC-41.2 as a yellow solid which was used in the next step without further purification . 990.0 mg, 94% yield. MS ( _APCI ): _Calcd for Formula _C29H20F3NO4 ([M+H]+) = 504 Found _: 504. ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) 8.67 (d, J = 8.0 Hz, 1H), 8.61 (d, J = 8.0 Hz, 1H), 8.27 (d, J = 2.4 Hz, 1H), 8.08 ( d, J = 8.0 Hz, 1H), 7.80 (m, 5H), 7.52 (d, J = 8.4 Hz, 1H), 7.38 (d, J = 8.4 Hz, 1H), 4.22 (t, J = 7.2 Hz, 2H), 3.73 (t, J = 6.0 Hz, 2H), 1.84 (m, 4H).

General procedure for the synthesis of compound PLC-41.3—4- (1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-1H-𠮿 of 4-methylbenzenesulfonic acid And[2,1,9-def]isoquinolin-2(3H)-yl)butyl ester: A 100 mL flask was fitted with a stir bar. Compound PLC-41.2 (200.0 mg, 0.40 mmol) and DCE (20 ml) were added to the flask. The solution was degassed at room temperature. p-Toluenesulfonic anhydride (519.0 mg, 1.6 mmol) and TEA (221.0 μL, 1.6 mmol) were added. The solution was then heated up to 90°C and kept at this temperature for 4 hours. TLC and LCMS were used to monitor the reaction. Add more DCE (20 mL), p-toluenesulfonic anhydride (519.0 mg, 1.6 mmol). The reaction was cooled to room temperature. Add _H2O (100 ml), TEA (221.0 μL, 1.6 mmol). The reaction was kept at 90°C overnight. After adding H ₂ O (150 ml) to stop the reaction, the mixture was extracted with DCM (150 ml *3). The combined organic phases were dried over _{anhydrous Na2SO4} and concentrated under vacuum evaporator to give PLC-41.3 as a yellow solid which was used in the next step without further purification. MS (APCI) _: Calculated for Formula: _C36H26F3NO6S ([MH]-) _{= 657} Found: 657. ¹ H NMR (400 MHz, CDCl ₃ ) 8.55 (d, J = 8.0 Hz, 1H), 8.51 (d, J = 8.0 Hz, 1H), 8.16 (d, J = 2.0 Hz, 1H), 7.92 (d, J = 8.0 Hz, 1H), 7.76 (m, 7H), 7.41 (d, J = 8.4 Hz, 1H), 7.32 (d, J = 8.0 Hz, 2H), 7.24 (d, J = 8.0 Hz, 1H) , 4.10 (m, 4H), 2.42 (s, 3H), 1.76 (m, 4H).

General procedure for the synthesis of compound PLC-41.4 — 2,6-dichloro-4-(4-(1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-1H-𠮿 And[2,1,9-def]isoquinolin-2(3H)-yl)butoxy)benzaldehyde: put into a 25 ml vial containing PLC-41.3 (131.5 mg, 0.20 mmol) and 4-hydroxyl -2,6-Dichlorobenzaldehyde (42.0 mg, 0.22 mmol) in DMF (5 mL). The solution was degassed at room temperature and _K2CO3 (41.4 mg, 0.30 mmol) _was added. The reaction was further degassed at room temperature. It was then warmed up to 65°C and kept stirring at this temperature overnight. TLC (50% EtOAc in hexanes) showed the reaction was complete. The reaction mixture was purified by flash chromatography on silica gel using EtOAc/hexane (5% to 40%) as eluent to give pure compound PLC-41.4 as a yield solid, 27.0 mg, 20% yield over 2 steps . _MS ( _APCI ) _: Calculated for Formula: _{C36H22Cl2F3NO5} ([MH]-) = ₆₇₆ Found: 676. ¹ H NMR (400 MHz, CDCl ₃ ) δ 10.37 (s, 1H), 8.67 (d, J = 8.0 Hz, 1H), 8.63 (d, J = 8.0 Hz, 1H), 8.26 (d, J = 2.4 Hz , 1H), 8.05 (d, J = 8.0 Hz, 1H), 7.78 (bs, 4H), 7.75 (m, 1H), 7.49 (d, J = 8.0 Hz, 1H), 7.35 (d, J = 8.0 Hz , 1H), 6.88 (s, 2H), 4.26 (m, 2H), 4.09 (m, 2H), 1.96 (m, 4H).

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-18l4 ,19l4-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-(trifluoromethane Base) phenyl) -1H-𠮿 And[2,1,9-def]isoquinoline-1,3(2H)-dione: Install an air condenser and a stirring bar in a 50 mL 2-necked round bottom flask. To the flask was 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, then p-TsOH•H ₂ O (0.2 mg, 0.002 mmol) was added. The reaction solution was kept at this temperature for 2 hours. Then DDQ (5.0 mg, 0.02 mmol) was added. The reaction was maintained at this temperature for 1 hour. Then BF3•OEt ₂ (59 μL, 0.48 mmol) and Et ₃ N (44 μL, 0.32 mmol) were added at room temperature. The reaction mixture was kept at room temperature overnight. The reaction mixture was loaded on silica gel and purified by flash chromatography using EtOAc/DCM (0 to 3%) as eluent to give pure PLC-41 as a dark purple solid, 12.0 mg, 28% yield. MS ( _APCI ) _{: Calculated} for _Formula : _{C62H43BCl2F5N3O4} ([MH]-) = ₁₀₇₀ Found: 1070. ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) 8.69 (d, J = 8.0 Hz, 1H), 8.64 (d, J = 8.0 Hz, 1H), 8.28 (d, J = 2.4 Hz, 1H), 8.09 ( d, J = 8.0 Hz, 1H), 8.05 (m, 2H), 7.79 (m, 5H), 7.53 (d, J = 8.0 Hz, 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).

Synthesis of compound PLC-42 General procedure for the synthesis of compound PLC-42.1 — 9-bromo-2-(2-(2-(2-hydroxyethoxy)ethoxy)ethyl)-1H-𠮿 And[2,1,9-def]isoquinoline-1,3(2H)-dione: Install a 100 mL flask with a stir bar. Into the flask, compound Ex-4.3 (1.3 g, 3.4 mmol), 2-(2-(2-aminoethoxy)ethoxy)ethan-1-ol in DMF (25 ml) (1.0 g, 6.8 mmol) and DMAP (29.0 mg, 0.24 mmol) were degassed at room temperature. The reaction mixture was heated up to 165°C and the reaction was maintained at this temperature for 2 hours. TLC and LCMS showed the reaction was complete. The reaction was cooled down to 50 °C. The solution was poured into a pre-cooled acetone (100 ml) solution with 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 by H ₂ O (150 ml) and further dried in a vacuum oven at 100° C. for 3 hours to give PLC-42.1 as a brown solid which was used in the next step without further purification. 805.0 mg, 48% yield. MS (APCI): Calculated for Formula: _C24H20BrNO6 ([MH]-) = ₄₉₈ Found: ₄₉₈ . ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) 8.61 (d, J = 8.0 Hz, 1H), 8.58 (d, J = 8.0 Hz, 1H), 8.18 (d, J = 2.4 Hz, 1H), 7.91 ( 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) , 4.42 (t, J = 6.0 Hz, 2H), 3.83 (t, J = 6.0 Hz, 2H), 3.63 (m, 8H).

General procedure for the synthesis of compound PLC-42.2—2- (2-(2-(2-hydroxyethoxy)ethoxy)ethyl)-9-(4-(trifluoromethyl)phenyl)-1H- 𠮿 And[2,1,9-def]isoquinoline-1,3(2H)-dione: A 250 mL flask was fitted with a stir bar. To the flask, compound 1621-36 (800.0 mg, 1.6 mmol), 4-(trifluoromethyl)phenylboronic acid in THF/DMF/H ₂ O (44 ml/ 8.8 ml/ 4.4 ml) was added (609.8 mg, 3.2 mmol), Pd(dppf)Cl ₂ (82.4 mg, 0.1 mmol) and K ₂ CO ₃ (600.0 mg, 4.4 mmol) were degassed at room temperature. The reaction mixture was heated up to 80 °C and the reaction was kept at this temperature overnight. TLC was used to monitor the reaction. Upon completion, the reaction was worked up by addition of _H2O (150 ml) to precipitate the product. The precipitate was collected by filtration. The solid was washed by H ₂ O (200 ml) and MeOH (20 ml), and further dried in a vacuum oven at 100° C. for 3 hours to give PLC-42.2 as a yellow solid which was used in the next step without further purification . Quantitative yield. MS (APCI _{): Calculated for Formula: C31H24F3NO6 (} [M+H]+) ₌ 564 Found _: 564. ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) 8.67 (d, J = 8.0 Hz, 1H), 8.61 (d, J = 8.0 Hz, 1H), 8.26 (d, J = 2.0 Hz, 1H), 8.07 ( d, J = 8.0 Hz, 1H), 7.96 (bs, 1H), 7.80 (m, 5H), 7.52 (d, J = 8.4 Hz, 1H), 7.37 (d, J = 8.4 Hz, 1H), 4.43 ( t, J = 6.0 Hz, 2H), 3.84 (t, J = 6.0 Hz, 2H), 3.70 (m, 2H), 3.64 (m, 4H), 3.54 (m, 2H).

General procedure for the synthesis of compound PLC-42.3—2- (2-(2-(1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-1H) of 4-methylbenzenesulfonic acid -𠮿 And[2,1,9-def]isoquinolin-2(3H)-yl)ethoxy)ethoxy)ethyl ester: A 100 mL flask was fitted 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 up to 90°C and kept at this temperature overnight. TLC and LCMS were used to monitor the reaction. Even with extended time, the reaction stayed at 90 conversion. After adding more p-toluenesulfonic anhydride (130.0 mg), the conversion could be increased to 97%. The reaction was cooled to room temperature. _H2O (100 ml) was added. The mixture was extracted with DCM (150 ml *3). The combined organic phases were dried over _{anhydrous Na2SO4} and concentrated under vacuum evaporator to give PLC-42.3 as a yellow solution (with NMP as residue), which was used in the next step without further purification. MS (APCI) _: Calculated for Formula _{: C38H30F3NO8S} ([MH]-) = ₇₁₇ Found: 717. ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) 8.64 (d, J = 8.0 Hz, 1H), 8.58 (d, J = 8.0 Hz, 1H), 8.26 (d, J = 2.4 Hz, 1H), 8.06 ( d, J = 8.0 Hz, 1H), 7.76 (m, 7H), 7.51 (d, J = 8.4 Hz, 1H), 7.34 (m, 3H), 4.38 (t, J = 6.0 Hz, 2H), 4.05 ( m, 2H), 3.76 (t, J = 6.0 Hz, 2H), 3.61 (m, 4H), 3.54 (m, 2H), 2.42 (s, 3H).

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-𠮿 and[2,1,9-def]isoquinolin-2(3H)-yl)ethoxy)ethoxy)ethoxy)benzaldehyde: Into a 25 ml vial, add 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 _K2CO3 (53.8 mg, 0.39 mmol) _was added. The reaction was further degassed at room temperature. It was then warmed up to 65°C and kept stirring at this temperature overnight. TLC (50% EtOAc in hexanes) showed the reaction was complete. The reaction mixture was purified by flash chromatography on silica gel using EtOAc/hexane (0% to 40% to 60%) as eluent to give pure compound PLC-42.4 as a yield solid, 37.0 mg, over 2 steps 19 %Yield. MS (APCI _{) : Calculated} for Formula: _{C38H26Cl2F3NO7} ([MH]-) = ₇₃₆ Found: 736. ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) δ 10.20 (s, 1H), 8.62 (d, J = 8.0 Hz, 1H), 8.57 (d, J = 8.0 Hz, 1H), 8.20 (d, J = 2.0 Hz, 1H), 8.01 (d, J = 8.0 Hz, 1H), 7.80 (s, 4H), 7.76 (dd, J = 8.0 Hz, 2.0 Hz, 1H), 7.47 (d, J = 8.0 Hz, 1H ), 7.33 (d, J = 8.0 Hz, 1H), 6.69 (s, 2H), 4.45 (t, J = 6.0 Hz, 2H), 3.86 (m, 4H), 3.72 (m, 6H).

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-18l4,19l4-Benzo[3',4']cyclohepta[1',2':4,5]pyrrolo[1,2-c]benzo[3',4']ring Hepta[1',2':4,5]pyrrolo[2,1-f][1,3,2]diazaborin-9-yl)phenoxy)ethoxy)ethoxy )ethyl)-9-(4-(trifluoromethyl)phenyl)-1H-𠮿 And[2,1,9-def]isoquinoline-1,3(2H)-dione: Install an air condenser and a stirring bar in a 100 mL 2-neck round bottom flask. To the flask was 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, then p-TsOH•H ₂ O (0.3 mg, 0.003 mmol) was added. The reaction solution was kept at this temperature for 2 hours. Then DDQ (6.2 mg, 0.03 mmol) was added. The reaction was maintained at this temperature for 1 hour. Then BF3•OEt ₂ (74 μL, 0.6 mmol) and Et ₃ N (56 μL, 0.4 mmol) were added at room temperature. The reaction mixture was kept at room temperature overnight. The reaction mixture was loaded on silica gel and purified by flash chromatography using EtOAc/DCM (0 to 6%) as eluent to give pure PLC-42 as a dark purple solid, 7.0 mg, 13% yield. MS (APCI): _Calculated for Formula: _{C64H47BCl2F5N3O6 (} [MH]-) = _{1130 Found} : ₁₁₃₀ . ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) 8.68 (d, J = 8.0 Hz, 1H), 8.63 (d, J = 8.0 Hz, 1H), 8.26 (d, J = 2.4 Hz, 1H), 8.08 ( d, J = 8.0 Hz, 1H), 8.04 (m, 2H), 7.78 (bs, 4H), 7.78 (dd, J = 8.0 Hz, 2.0 Hz, 1H), 7.50 (d, J = 8.0 Hz, 1H) , 7.37 (m, 5H), 7.29 (m, 2H), 7.07 (s, 2H), 6.46 (s, 2H), 4.46 (t, J = 8.4 Hz, 2H), 4.13 (t, J = 4.4 Hz, 2H), 3.86 (m, 4H), 3.74 (m, 4H), 2.63 (m, 4H), 2.31 (bs, 4H), 2.04 (m, 4H).

Synthesis of compound PLC-43 Synthesis of compound PLC-43 General procedure for the synthesis of compound PLC-43.1 — 2-(3-hydroxypropyl)-9-(perfluorophenyl)-1H-𠮿 And[2,1,9-def]isoquinoline-1,3(2H)-dione: Install a 100 mL flask with a stir bar. To the flask, compound PLC-38.1 (400.0 mg, 0.9 mmol), (perfluorophenyl)boronic acid (240.0 mg, 1.1 mmol), Pd ₂ (dba) ₃ (43.0 mg, 0.05 mmol), CsF (285.6 mg, 1.9 mmol), Ag ₂ O (259.4 mg, 1.1 mmol) and (t-Bu) ₃ P (1.9 ml, 1.9 mmol) were degassed at room temperature. The reaction mixture was heated up to 80 °C and the reaction was kept at this temperature overnight. TLC was used to monitor the reaction. Upon completion, the reaction was purified by silica gel flash chromatography using EtOAc/hexane (5 to 10 to 50 to 70%) as eluent to give pure compound PLC-43.1 as a yellow solid, 136.0 mg, 28% Yield. MS _{( APCI} ): Calcd for Formula _C27H14F5NO4 ([MH] _- ) = 511 Found: 511. ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) 8.57 (d, J = 8.0 Hz, 1H), 8.55 (d, J = 8.0 Hz, 1H), 8.07 (s, 1H), 7.92 (d, J = 8.0 Hz, 1H), 7.53 (d, J = 8.0 Hz, 1H), 7.46 (d, J = 8.0 Hz, 1H), 7.32 (d, J = 8.0 Hz, 1H), 4.25 (t, J = 6.0 Hz, 2H), 3.48 (m, 2H), 3.07 (t, J = 6.8 Hz, 1H), 1.90 (m, 2H).

General procedure for the synthesis of compound PLC-43.2 — 2-(3-bromopropyl)-9-(perfluorophenyl)-1H-𠮿 And[2,1,9-def]isoquinoline-1,3(2H)-dione: Install a 100 mL flask 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. TLC and LCMS were used to monitor the reaction. Upon completion, the reaction was purified by silica gel flash chromatography using EtOAc/hexane (5 to 10 to 50 to 70%) as eluent to give pure compound PLC-43.2 as a yellow solid, 116.0 mg, 76% Yield. MS (APCI): _Calcd . for _{C27H13BrF5NO3} ([M+H]+) = ₅₇₃ Found: ₅₇₃ . ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) 8.64 (d, J = 8.0 Hz, 1H), 8.61 (d, J = 8.0 Hz, 1H), 8.15 (d, J = 1.6 Hz, 1H), 7.99 ( d, J = 8.0 Hz, 1H), 7.61 (m, 1H), 7.54 (d, J = 8.0 Hz, 1H), 7.39 (d, J = 8.0 Hz, 1H), 4.32 (t, J = 6.8 Hz, 2H), 3.54 (t, J = 6.8 Hz, 2H), 2.34 (quintet, J = 6.8 Hz, 2H).

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-18l4 ,19l4-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-(perfluorophenyl)- 1H-𠮿 And[2,1,9-def]isoquinoline-1,3(2H)-dione: To a 25 ml vial, add PLC-1.3 (73.4 mg, 0.1 mmol), PLC-43.2 (60.0 mg, 0.1 mmol ), K ₂ CO ₃ (28.7 mg, 0.2 mmol) and DMF (2 ml). The mixture was sonicated for 2 min at room temperature. It was then warmed up to 75°C and kept stirring at this temperature for 4 hours. TLC (50% EtOAc in hexanes) showed the reaction was complete. The reaction mixture was purified by flash chromatography on silica gel using EtOAc/hexanes (0 to 3%) as eluent to afford pure compound PLC-43 as a dark purple solid, 91.0 mg, 81% yield. MS (APCI) _{: Calcd for Formula: C60H37BCl2F7N3O4 (} [MH] _- ) = 1077 _Found : 1077. ¹ H NMR (400 MHz, CDCl ₂ CDCl ₂ ) 8.67 (d, J = 8.0 Hz, 1H), 8.63 (d, J = 8.0 Hz, 1H), 8.18 (bs, 1H), 8.05 (m, 2H), 8.01 (d, J = 8.0 Hz, 1H), 7.61 (m, 1H), 7.54 (d, J = 8.0 Hz, 1H), 7.38 (m, 5H), 7.30 (m, 2H), 7.02 (s, 2H ), 6.47 (s, 2H), 4.44 (t, J = 6.0 Hz, 2H), 4.22 (t, J = 6.0 Hz, 2H), 2.64 (m, 4H), 2.32 (m, 6H), 2.05 (m , 4H).

Synthesis of compound PLC-44 Compound PLC-44.1 : 9-(3,5-bis(trifluoromethyl)phenyl)-2-(3-hydroxypropyl)-1H-𠮿 And[2,1,9-def]isoquinoline-1,3(2H)-dione: Compound PLC-38.1 (0.4241 g, 1.0 mmol, 1 eq) was suspended in DMF (5 ml), H ₂ O (0.5 ml), add (bis-3,5-trifluoromethyl)phenylboronic acid (0.51586 g, 2.0 mmol, 2 eq), K ₂ CO ₃ (0.27642 g, 2.0 mmol, 2 eq), Pd(dppf ) _Cl2DCM (16.33 mg, 0.02 mmol, 0.02 eq). The resulting mixture was Vac-Fill argon circulated 3 times, stirred and heated at 80°C for 45 minutes, the mixture became viscous, 15 ml DMF was added and stirring was continued at 80°C for another 15 minutes. The reaction mixture was cooled to room temperature, concentrated by evaporator, water was added to the residue mixture and kept at RT for 1 h. The precipitate was filtered to give 570 mg of a cyan-yellow solid, which was washed with MeOH to give 270 mg of pure product. Yield 48%. MS (APCI) _: Calcd for Formula: _C29H17F6NO4 (M-) _{= 557} ; found: 557. ¹ H NMR (400 MHz, ) δ 8.60 (d, J = 7.9 Hz, 1H), 8.55 (d, J = 8.4 Hz, 1H), 8.17 (d, J = 2.2 Hz, 1H), 8.03 (d, J = 8.1 Hz, 1H), 8.00 (s, 2H), 7.87 (s, 1H), 7.70 (dd, J = 8.7, 2.1 Hz, 1H), 7.47 (d, J = 8.6 Hz, 1H), 7.31 (d , J = 8.3 Hz, 1H), 4.25 (t, J = 6.2 Hz, 2H), 3.49 (d, J = 6.1 Hz, 3H), 3.08 (t, J = 6.8 Hz, 1H), 1.90 (t, J = 6.0 Hz, 2H).

Compound PLC-44.2 : 9-(3,5-bis(trifluoromethyl)phenyl)-2-(3-bromopropyl)-1H-𠮿 And[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 borrowed Heat to reflux at 130°C for 16 hours by heating block. LCMS showed >90% conversion. After cooling to RT, the solid was filtered, washed with water, and dried in a vacuum oven to give the desired compound with some unreacted SM. Obtained 600 mg of cyan-yellow solid with a yield of 86%. The product was used in the next step without further purification. MS (APCI) _{: Calcd. for Formula: C29H16BrF6NO34 (} M-) = ₆₂₀ ; found 620. ¹ H NMR (400 MHz) δ 8.58 (d, J = 7.8 Hz, 1H), 8.53 (d, J = 8.4 Hz, 1H), 8.16 (d, J = 2.3 Hz, 1H), 8.04 - 7.97 (m, 2H), 7.86 (s, 1H), 7.70 (dd, J = 8.6, 2.2 Hz, 1H), 7.46 (d, J = 8.6 Hz, 1H), 7.30 (d, J = 8.3 Hz, 1H), 4.23 ( t, J = 7.1 Hz, 2H), 3.45 (t, J = 6.8 Hz, 2H), 2.34 - 2.16 (m, 2H).

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-18l4,19l4-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-𠮿 And[2,1,9-def]isoquinoline-1,3(2H)-dione: Compound PLC-44.2 (46.52 mg, 0.075 mmol, 1.15 eq) was suspended in anhydrous DMF (2.0 ml), added PLC-1.3 (38.04 mg, 0.065 mmol, 1 eq), _K2CO3 (20.73 mg, 0.15 mmol, 2.3 eq), _NaI (4.15 mg, catalytic amount). The resultant was stirred at 85 °C for 3 hours under argon atmosphere. The mixture was filtered, the solid was washed with 50 ml of water, then loaded onto a 40 g column, 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 . Yield 62%. MS _{( APCI} ) _: Calcd for Formula: _{C62H40BCl2F8N3O4} (M-) = ₁₁₂₄ ; found _: 1124. ¹ H 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 = 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 = 8.3 Hz, 1H), 7.27 (dt, J = 7.4, 3.7 Hz, 3H), 7.23 - 7.15 (m, 2H), 6.92 (s, 2H), 6.38 (s, 2H), 4.36 (t, J = 7.0 Hz, 2H), 4.13 (t, J = 6.0 Hz, 2H), 2.54 (t, J = 6.8 Hz, 4H), 2.24 (s, 4H), 1.96 (t, J = 7.2 Hz, 4H).

Synthesis of compound PLC-45 : Compound PLC-45.1 : 4'-(tert-butyl)-3-nitro-[1,1'-biphenyl]-4-ol: at room temperature, 4-bromo-2-nitro-phenol (5.45 g, 25.0 mmol) and 4-(tert-butyl)phenylboronic acid (5.563 g, 31.25 mmol) were dissolved in dioxane (100 mL) and stirred for 5 minutes. After a clear solution formed, Pd( _PPh3 ) _2Cl2 (0.175 g, 0.25 mmol) and _4N aqueous _K2CO3 (25.0 ml, 50 mmol, 2 eq) were added rapidly; _the mixture was circulated through Vac-Fil nitrogen Degassed 3 times, then heated at 80° C. for 4 hours. After cooling the reaction to RT, the pH was adjusted to 5-6 with 4N aqueous HCl, extracted with ethyl acetate (250 mL), and passed through a short pad of Celite. The pad was washed with EA (150 ml x2). The organic layers were combined and washed with brine (25 mL), dried over anhydrous MgSO ₄ , 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 obtain 3.8 yellow solids, yield 56%. MS (APCI) _: Calcd. for Formula: _C16H17NO3 (M-) = ₂₇₁ ; found: 271. ¹ H 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).

Compound PLC-45.2 : 4-bromonaphthalic anhydride (10 g, 36 mmol, 1.15 eq), 4'-(tert-butyl)-3-nitro-[1,1'-biphenyl]-4 -Alcohol ( PLC-45.1 ) (8.5 g, 31.32 mmol, 1 eq), NaOH (0.864 g, 21.6 mmol, 0.6 eq) were mixed in anhydrous NMP (65 mL), copper powder (1.371 g, 21.6 mmol, 0.6 eq), the resulting mixture was degassed by Vac-Fil nitrogen cycles 3 times, then heated and stirred at 145 °C under _N2 atmosphere for 5 h, then overnight at RT. The reaction mixture was treated with aqueous HCl; after standing at RT for 12 hours, a brown solid precipitated, filtered, and washed with hot MeOH (250 ml x 3) to give (10.8 g, 23.1 mmol) a light brown solid, yield 73%, purity 86%. MS (APCI) _: Calcd. for Formula: _C28H21NO6 (M-) = ₄₆₇ ; found: 467.

Compound PLC-45.3 : 6-((3-amino-4'-(tert-butyl)-[1,1'-biphenyl]-4-yl)oxy)-1H,3H-benzo[de ] Isodione-1,3-dione: To PLC-45.2 (4.885g, 10.45 mmol, 1.0 eq) in 2-MeTHF (70.0 mL) and HCl (4 M, 26.1 mL, 10 eq) To the mixture was added SnCl ₂ .2H ₂ O (9.4 g, 41.75 mmol, 4.0 eq) in one portion. The mixture was stirred at 90 °C for 1/2 hour. TLC (hexane/ethyl acetate = 7:3) and LCMS showed the reaction was complete. The white solid was filtered off and washed with EA/2-MeTHF (1:1) (100 mL x 2). The combined organic filtrates were washed with water, separated and concentrated under reduced pressure to give a sticky solid residue. The crude product was washed with 100 mL of hot water at 50 °C for 1/2 hour, filtered, and then dried under reduced pressure to give PLC-45.3 (4.5 g, 10.28 mmol) as a yellow-brown solid. 98% yield. MS (APCI): Calcd for Formula: _C28H23NO4 (M-) ₌ 437; Found: ₄₃₇

Compound PLC-45.4 : 9-(4-(tert-butyl)phenyl)-1H,3H-iso[6,5,4-mna]𠮿 -1,3-Diketone: To compound PLC-45.3 (1.844 g, 4.215 mmol, 1.0 eq) in AcOH (28.5 mL) and _H2O (9.0 mL) was added conc. HCl dropwise at 0 °C ( 2.445 mL) and H ₂ O (9 mL) containing NaNO ₂ (2.9 g, 42.15 mmol, 10 eq) and stirred at 0° C. for 1 hour. The above solution was added to CuSO ₄ 5H ₂ O (4.35 g, 17.42 mmol, 4.1 eq) in H ₂ O (175 ml), AcOH (11 ml) via dropping funnel at 130° C. over a period of ½ hour . After the addition was complete, the resultant was continued to be stirred at the same temperature 130° C. for another 15 minutes. The mixture was filtered and washed with H ₂ O (3 x 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 ₎ : Calcd for Formula: _C28H20O4 (M-) = 420; Found: ₄₂₀

Compound PLC-45.5 : 9-(4-(tert-butyl)phenyl)-2-(3-hydroxypropyl)-1H-𠮿 And[2,1,9-def]isoquinoline-1,3(2H)-dione: Add compound PLC-45.4 (0.420 g, 1.0 mmol, 1.0 eq) to anhydrous DMSO (4 mL) was added 3-amino-1-propanol (0.300 g, 4.0 mmol, 4.0 eq) and the resulting mixture was stirred at 130°C over a period of 45 minutes. After completing the reaction, DMSO was removed by filtration. The solid was washed with water (50 ml x 3) and dried in a vacuum oven to achieve 0.45 g of yellow solid; 94% yield. MS (APCI): Calcd for Formula: _C31H27NO4 (M-) _{= 477} ; found: 477. ¹ H 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 = 8.2 Hz, 2H), 7.45 (d, J = 8.6 Hz, 1H), 7.32 (d, J = 8.3 Hz, 1H), 6.50 (s, 2H), 4.42 (t, J = 6.9 Hz, 2H), 4.17 ( t, J = 6.2 Hz, 2H), 2.54 (s, 6H), 2.28 (s, 2H), 1.40 (s, 9H).

Compound PLC-45.6 : 2-(3-bromopropyl)-9-(4-(tert-butyl)phenyl)-1H-𠮿 And[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 by The heating block was heated at 130°C for 8 hours. LCMS showed complete consumption of SM. The mixture was cooled to RT and stood at RT for 16 hours. The yellow solid was filtered, washed several times with water, dried in a vacuum oven to give 0.275 g, yield 96%. The product was used in the next step without further purification. MS ( _APCI ) _: Calcd. for Formula: _C31H26BrNO3 (M-) = 540; found: 540. ¹ H 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 = 8.0 Hz, 1H) , 7.72 (d, J = 8.7 Hz, 1H), 7.55 (d, J = 8.0 Hz, 2H), 7.45 (d, J = 8.0 Hz, 2H), 7.41 (d, J = 8.5 Hz, 1H), 7.29 (d, J = 8.4 Hz, 1H), 4.25 (s, 2H), 3.48 (d, J = 6.1 Hz, 2H), 3.16 (d, J = 6.8 Hz, 1H), 1.90 (s, 2H), 1.31 (s, 9H).

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-18l4,19l4-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-𠮿 And[2,1,9-def]isoquinoline-1,3(2H)-dione: Compound PLC-45.6 (40.53 mg, 0.075 mmol, 1.15 eq) was suspended in dry DMF (2.0 ml), added PLC-1.3 (38.04 mg, 0.065 mmol, 1 eq), _K2CO3 (20.73 mg, 0.15 mmol, 2.3 eq), _NaI (4.15 mg, catalytic amount). The resulting mixture was stirred at 85 °C for 4 h under an atmosphere of argon. DMF and water were removed by evaporator at 53°C; the residue was washed with 50 ml hot water, then loaded onto a 40 g column with Hex:DCM (9:1 to DCM only (4CV)) then DCM /EtAco (99:1), the product from column chromatography purification was washed with hot water to afford 27 mg of a dark purple solid, yield 38.5%. MS (APCI) _: Calcd _. for Formula: _{C64H50BCl2F2N3O4} (M- ₎ = ₁₀₄₄ ; found _: 1044. ^1H 1H 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 = 8.4 Hz, 1H), 7.33 - 7.29 (m, 3H), 7.22 (d, J = 7.1 Hz, 2H), 6.95 (s, 2H), 6.42 (s, 2H), 4.47 (t, J = 6.8 Hz, 2H), 4.21 (t, J = 6.0 Hz, 2H), 2.62 (t, J = 6.8 Hz, 4H), 2.40 - 2.24 (m, 4H), 2.09 - 1.97 (m, 4H), 1.39 (s, 9H).

Synthesis of compound PLC-46 : Compound PLC-46.2 : 9-(3,5-bis(trifluoromethyl)phenyl)-2-(2-hydroxyethyl)-1H-𠮿 And[2,1,9-def]isoquinoline-1,3(2H)-dione: Step 1: Combine Ex-4.3 (0.735 g, 2.0 mmol, 1.0 eq) and 3-amino-1-ethanol (0.732 g, 12.0 mmol, 6.0 eq) of the mixture was placed in a 20 mL vial and sealed with a septum cap. The resulting mixture was stirred at 160°C over a period of 45 minutes. After cooling to RT, the reaction was stirred with MeOH (10 mL) at RT for 15 min, then filtered. The crude product PLC-46.1 was used in the next step without further purification. MS (APCI): Calcd. for Formula: _C20H12BrNO4 (M-) = 410; _{found :} 410. ¹ 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 RT, the crude product from the above step was mixed with DMF (5 ml), H ₂ O (0.5 ml), (bis-3,5-trifluoromethyl)phenylboronic acid (1.031 g, 4.0 mmol, 2 eq), K ₂ CO ₃ (0.553 g, 4.0 mmol, 2 eq), Pd(dppf)Cl ₂ DCM (32.66 mg, 0.04 mmol, 0.02 eq) mixed, Vac-Fill argon cycle 3 times, at 80°C After stirring and heating for 45 minutes, the mixture became viscous, 5 ml DMF was added and stirring was continued at 80 °C for another 15 minutes. The reaction mixture was cooled to room temperature, concentrated by evaporator, water was added to the reaction mixture, kept at RT for 1 h, the precipitate was filtered to obtain 1.1 g of a cyan-yellow solid, which was washed with MeOH to obtain 0.85 g of the The desired product, PLC-46.2 . The yield is 80%. MS (APCI): _Calcd for Formula: _C28H15F6NO4 ( _M- ) ₌ 543; found: 543. ¹ H 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).

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-18l4,19l4-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)-1H-𠮿 And[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) was dissolved in anhydrous toluene (2 mL); a solution of 0.15 ml 1M DIAD/toluene + 1 mL anhydrous toluene was added dropwise over 15 min at room temperature. The resulting mixture was stirred under argon atmosphere for 16 hours. Additional triphenylphosphine (19.73 mg, 0.075 mmol) and 0.075 ml 1M DIAD/toluene + 0.5 mL anhydrous toluene were added successively and the mixture was stirred for a further 8 hours. Purification: The RX mixture was loaded onto a 80 g SiO ₂ column and eluted using Hex:DCM (7:3), (1:4), then only DCM, and the 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 brown purple solid; 42% yield. MS ( _APCI ) _: Calculated for Formula: _{C61H38BCl2F8N3O4} ( _M- ) = ₁₁₁₀ , _found : 1110. ¹ H 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, 2.2 Hz, 1H), 7.53 (d, J = 8.6 Hz, 1H ), 7.38 (d, J = 8.3 Hz,1H), 7.35 - 7.26 (m, 4H), 7.21 (dd, J = 6.8, 2.0 Hz, 2H), 7.11 (s, 2H), 6.39 (s, 2H) , 4.72 (t, J = 6.2 Hz, 2H), 4.43 (t, J = 6.2 Hz, 2H), 2.61 (t, J = 6.8 Hz, 4H), 2.29 (s, 4H), 2.02 (q, J = 6.8 Hz, 4H).

Synthesis of compound PLC-47 : Compound PLC-47.1 : (9-bromo-2-(6-hydroxyhexyl)-1H-𠮿 and[2,1,9-def]isoquinoline-1,3(2H)-dione): Compound Ex-4.3 (6.534 mmol, 2.401g), 6-aminohexan-1-ol (13.08 mmol , 1533 mg) and DMAP (1.962 mmol, 240 mg) and DMF combined. The crude product was filtered off and washed with water, then the wet precipitate was used in the next step without further purification. MS (APCI): Calcd for Formula: _C24H20BrNO4 (M+H) = 466; _found : ₄₆₆ .

Compound PLC-47.2 : (2-(6-hydroxyhexyl)-9-(4-(trifluoromethyl)phenyl)-1H-𠮿 and[2,1,9-def]isoquinoline-1,3(2H)-dione): at 80°C, in THF (120 mL)/DMF (24 mL) Compound PLC-47.1 (assumed 100% yield, 6.534 mmol, 3.047 g), (4-(trifluoromethyl)phenyl)boronic acid (13.068 mmol, 2.482 g ₎ in /H 2 O (12 mL), K ₂ CO ₃ (17.969 mmol, 2483 mg) and Pd(dppf)Cl ₂ (0.4574 mmol, 335 mg) were combined. After adding water and filtering, the resulting precipitate was washed with water, then methanol. The product was dried by suction and then in vacuo. Obtained 1.191 g (34% yield based on compound 29.3 over 2 steps). MS (APCI) _{: Calcd} for Formula: _C31H24F3NO4 (M+H) = ₅₃₂ ; found: 532.

Compound PLC-47.3 : (2-(6-bromohexyl)-9-(4-(trifluoromethyl)phenyl)-1H-𠮿 And [2,1,9-def]isoquinoline-1,3(2H)-dione): Put a stir bar into 250 mL 2N RBF and install gas adapter/fin condenser and flow controller. Compound PLC-47.2 (2.239 mmol, 1.190 g) was added to the flask, followed by 48% HBr/H ₂ O (30 mL). The heat block was set to 130°C and the reaction mixture was stirred at this temperature for 3 hours. Another portion of 48% HBr/ _H2O (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 (about 100 mL), then the precipitate was filtered off, washed with water and then methanol. The product was loaded onto approximately 25 g of silica gel in the loader. Purified by flash chromatography on silica gel (120 g, solids load, equilibration 0% EtOAc/DCM, 0% (2 CV) to 10% EtOAc/DCM (20 CV)). Fractions bearing product were collected and evaporated to dryness in vacuo. About 80% pure material was obtained. A yellow solid was obtained, 1.073 g (80% yield). MS (APCI) _: Calcd for Formula: _{C31H23BrF3NO3} (M+H) = ₅₉₄ ; _found : 594. ¹ H NMR (400 MHz, TCE) δ 8.63 (d, J = 7.9 Hz, 1H), 8.58 (d, J = 8.3 Hz, 1H), 8.23 (d, J = 2.1 Hz, 1H), 8.03 (d, J = 8.0 Hz, 1H), 7.84 - 7.73 (m, 5H), 7.49 (d, J = 8.6 Hz, 1H), 7.34 (d, J = 8.3 Hz, 1H), 4.19 - 4.09 (m, 2H), 3.44 (td, J = 6.8, 1.9 Hz, 2H), 1.90 (p, J = 6.9 Hz, 2H), 1.75 (p, J = 7.8 Hz, 2H), 1.57 - 1.38 (m, 4H).

Compound PLC-47.4 : (2,6-dichloro-4-((6-(1,3-dioxo-9-(4-(trifluoromethyl)phenyl)-1H-𠮿 and[2,1,9-def]isoquinolin-2(3H)-yl)hexyl)oxy)benzaldehyde): compound PLC-47.4 was self-contained in anhydrous DMF (10 mL) in a similar manner to compound 34.4 Compound PLC-47.3 (0.200 mmol, 119 mg), 2,6-dichloro-4-hydroxybenzaldehyde (0.300 mmol, 57 mg) and K ₂ CO ₃ (0.260 mmol, 36 mg) were synthesized. The crude compound was dissolved in DCM and loaded onto ~5 g of silica gel in a loader. Purify by flash chromatography on silica gel (80 g, solids load, equilibrate 70% DCM/hexane, elute 70% (2 CV) to 100% DCM/hexane (5 CV) to isocratic 100% DCM/hexane Hexane (5 CV) to 0% EtOAc/DCM (0 CV) to isocratic 0% EtOAc/DCM (5 CV) to 10% EtOAc/DCM (20 CV)). Fractions containing product were evaporated to dryness in vacuo. Obtained a yellow solid, 113 mg, (60% yield). MS ₍ APCI) _{: Calcd} for Formula: _{C38H26Cl2F3NO5} (M+H) = 704; found _: 704. ¹ H NMR (400 MHz, TCE) δ 10.37 (s, 1H), 8.64 (d, J = 7.9 Hz, 1H), 8.59 (d, J = 8.4 Hz, 1H), 8.25 (d, J = 2.2 Hz, 1H), 8.05 (d, J = 8.0 Hz, 1H), 7.78 (dd, J = 11.2, 1.9 Hz, 5H), 7.50 (d, J = 8.6 Hz, 1H), 7.36 (d, J = 8.3 Hz, 1H), 6.92 (s, 2H), 4.23 - 4.11 (m, 2H), 4.02 (t, J = 6.4 Hz, 2H), 1.89 - 1.70 (m, 4H), 1.59 - 1.45 (m, 4H).

Compound PLC-47 : (2-(6-(3,5-dichloro-4-(19,19-difluoro-6,7,11,12,13,19-hexahydro-5H-18l4,19l4- 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)hexyl)-9-(4-(trifluoromethyl)phenyl )-1H-𠮿 and[2,1,9-def]isoquinoline-1,3(2H)-dione): Compound PLC-47 was obtained from compound PLC-47.4 (0.1164 mmol, 82 mg), 1 , 4,5,6-tetrahydrobenzo[6,7]cyclohepta[1,2-b]pyrrole (0.2444 mmol, 45 mg ( Ex-7.3 ) and pTsOH.H2O (0.0058 mmol, 1.1 mg), then DDQ (0.1989 mmol, 45 mg) and 2X Et3N (0.9312 mmol, 0.130 mL) and BF3.OEt2 (1.397 mmol, 0.172 mL) were synthesized in anhydrous DCM (20 mL) at room temperature and then at 50 °C. The crude reaction mixture was diluted with about 25% hexane, then loaded onto about 15 g of silica gel in a loader. Purified by flash chromatography on silica gel (80 g, solids load, equilibrated 70% DCM/hexane, eluting 70% (2 CV) to 100% DCM/hexane (5 CV) to isocratic 100% DCM/hexane (5 CV) to 100% DCM/hexane (isocratic) in 0.5% EtOAc modifier). Fractions containing product were evaporated to dryness in vacuo. Dark red solid was obtained, 79 mg (62% yield). MS (APCI): For formula: C ₆₄ H ₄₇ BCl ₂ F ₅ N ₃ O ₄ (M+ H) Calculated = 1098; found: 1098. ¹ H 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), 6.48 (s, 2H), 4.20 (t, J = 7.7 Hz, 2H), 4.06 (t, J = 6.3 Hz, 2H), 2.63 (t, J = 6.9 Hz, 4H), 2.42 - 2.19 (m, 4H), 2.08 - 2.00 (m, 2H), 1.88 (q, J = 7.3 Hz, 2H), 1.85 - 1.73 (m, 2H), 1.67 - 1.49 (m, 4H).

Synthesis of compound PLC-48 Compound PLC-48.2 (4-(2-(3-(3,5-dichloro-4-formylphenoxy)propyl)-1,3-dioxo-2,3-dihydro- 1H-𠮿 [2,1,9-def]isoquinolin-9-yl)tert-butylbenzoate): Compound PLC-48.2 was obtained from compound PLC contained in anhydrous DMF (10 mL) in a similar manner to the above procedure Synthesis of -48.1 (0.1471 mmol), 2,6-dichloro-4-hydroxybenzaldehyde (0.441 mmol, 84 mg) and K ₂ CO ₃ (0.4120 mmol, 57 mg). The crude reaction was diluted with crushed ice (ca. 50 g). Once it was all melted, the crude product was isolated by centrifugation. The product was dissolved in DCM and evaporated to dryness in vacuo. A yellow solid was obtained in quantitative yield. MS ( _APCI ) _: Calcd for Formula: _C39H29Cl2NO7 (M+H) = 694; found _: 694. ¹ H NMR (400 MHz, TCE) δ 10.37 (s, 1H), 8.64 (d, J = 7.9 Hz, 1H), 8.59 (d, J = 8.3 Hz, 1H), 8.28 (d, J = 2.2 Hz, 1H), 8.13 (d, J = 8.1 Hz, 2H), 8.07 (d, J = 8.0 Hz, 1H), 7.81 (dd, J = 8.6, 2.1 Hz, 1H), 7.75 (d, J = 8.2 Hz, 2H), 7.52 (d, J = 8.6 Hz, 1H), 7.38 (d, J = 8.3 Hz, 1H), 6.85 (s, 2H), 4.39 (t, J = 6.7 Hz, 2H), 4.18 (t, J = 5.9 Hz, 2H), 2.28 (p, J = 5.9 Hz, 2H), 1.64 (s, 9H).

Compound PLC-48 (4-(2-(3-(3,5-dichloro-4-(19,19-difluoro-6,7,11,12,13,19-hexahydro-5H-18l4, 19l4-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)-1,3-dioxo-2 ,3-Dihydro-1H-𠮿 and[2,1,9-def]isoquinolin-9-yl)tert-butylbenzoate): compound PLC-48 was obtained from compound PLC-48.2 (0.1471 mmol, 102 mg), 1,4,5,6-Tetrahydrobenzo[6,7]cyclohepta[1,2-b]pyrrole ( Ex-7.3 , 0.3090 mmol, 57 mg) and TFA (1% v/v), then DDQ (0.2501 mmol, 57 mg) and 2X Et ₃ N (1.177 mmol, 0.164 mL) and BF ₃ .OEt ₂ (1.765 mmol, 0.218 mL) in anhydrous DCM (20 mL) at room temperature, then at 50°C synthesis. The crude reaction mixture was diluted with hexane and loaded onto approximately 20 g of silica gel in a loader. Purified by flash chromatography on silica gel (220 g, solids load, equilibrate 10% EtOAc/hexane, elute 10% (2 CV) to 30% EtOAc/hexane (40 CV)). Fractions containing pure product were evaporated to dryness in vacuo. Obtained 80 mg (50% yield). _{MS (APCI): Calcd. for Formula: C65H50BCl2F2N3O6 ( M +} H) = _{1088 ;} found: 1088. ¹ H 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 = 8.6 Hz, 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 = 6.9 Hz, 2H), 4.22 (t, J = 6.0 Hz, 2H), 2.63 (t, J = 6.9 Hz, 4H), 2.40 - 2.24 (m, 6H), 2.11 - 2.00 (m, 4H), 1.62 (s, 9H).

Synthesis of compound PLC-49 : Compound PLC-49.1 (9-(4-butylphenyl)-2-(3-hydroxypropyl)-1H-𠮿 and[2,1,9-def]isoquinoline-1,3(2H)-dione): Compound PLC-49.1 was self-contained in THF (30 mL)/DMF (6 mL) in a similar manner to the above procedure Compound PLC-38.1 (1.500 mmol, 636 mg), (4-butylphenyl)boronic acid (3.00 mmol, 534 mg), K ₂ CO ₃ (4.125 mmol, 570 mg) and Pd in /water (3 mL) (dppf) _Cl2 (0.105 mmol, 77 mg) was synthesized at 80°C. The precipitated compound was filtered off, washed with water, and dried in vacuo. Obtained as a tan solid, 655 mg (92% yield). MS (APCI): Calcd for Formula: _C31H27NO4 (M+H) _{= 478} ; found: 478. ¹ H 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 = 6.1 Hz, 2H), 3.57 (q, J = 6.0 Hz, 2H), 3.24 (t, J = 6.9 Hz, 1H), 2.70 (t, J = 7.7 Hz, 2H), 2.06 - 1.92 (m, 2H), 1.75 - 1.64 (m, 2H), 1.42 (h, J = 7.4 Hz, 2H), 0.98 (t, J = 7.3 Hz, 3H).

Compound PLC-49.2 (4-methylbenzenesulfonic acid 3-(9-(4-butylphenyl)-1,3-dioxo-1H-𠮿 And [2,1,9-def]isoquinolin-2(3H)-yl)propyl ester): Place a 100 mL 2N round bottom flask in an aluminum heating block and place a stir bar. The flask was fitted with a finned condenser/gas adapter and 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 anhydrous DCE (20 mL). The reaction mixture was stirred at room temperature under argon and _Et3N (1.463 mmol, 0.20 mL) was added. The reaction mixture was stirred under argon and the heating block was set to 90°C and stirred at this temperature for 1 hour. The reaction was cooled to room temperature and loaded onto approximately 15 g of silica gel in a loader. Purified by flash chromatography on silica gel (80 g, solids load, equilibration 0% EtOAc/DCM, eluting 0% (2 CV) to 10% EtOAc/DCM (10 CV)). Fractions containing product were evaporated to dryness in vacuo. Obtained as a yellow solid, 157 mg (77% yield). MS ( _APCI ): _Calcd . for Formula: _C38H33NO6S (M+H) = 632; found: 632. ¹ H 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, 6.6 Hz, 4H), 2.70 (t, J = 7.8 Hz, 2H), 2.42 (s, 3H), 2.19 - 2.07 (m, 2H), 1.76 - 1.64 (m, 2H) , 1.42 (h, J = 7.3 Hz, 2H), 0.98 (t, J = 7.4 Hz, 3H).

Compound PLC-49.3 (4-(3-(9-(4-butylphenyl)-1,3-dioxo-1H-𠮿 and[2,1,9-def]isoquinolin-2(3H)-yl)propoxy)-2,6-dichlorobenzaldehyde): Compound PLC-49.3 was self-contained in a similar manner to the procedure above PLC-49.2 (0.122 mmol, 77 mg), 2,6-dichloro-4-hydroxybenzaldehyde (0.366 mmol, 70 mg) and K ₂ CO ₃ (0.341 mmol, 47 mg) in anhydrous DMF (10 mL) synthesis. The crude product was loaded onto about 15 g of silica gel in the loader. Purified by flash chromatography on silica gel (80 g, solids load, equilibration 0% EtOAc/DCM, eluting 0% (2 CV) to 10% EtOAc/DCM (10 CV)). Fractions containing product were evaporated to dryness in vacuo. Obtained as a yellow solid, 60 mg (76% yield). MS (APCI) _{: Calcd} . for Formula: _C38H29Cl2NO5 (M+H) = 650; _found : 650. ¹ H NMR (400 MHz, TCE) δ 10.37 (s, 1H), 8.63 (d, J = 7.9 Hz, 1H), 8.58 (d, J = 8.3 Hz, 1H), 8.26 (d, J = 2.1 Hz, 1H), 8.06 (d, J = 8.1 Hz, 1H), 7.79 (dd, J = 8.6, 2.1 Hz, 1H), 7.64 - 7.58 (m, 2H), 7.48 (d, J = 8.6 Hz, 1H), 7.36 (d, J = 7.2 Hz, 1H), 7.34 (d, J = 7.1 Hz, 2H), 6.85 (s, 2H), 4.39 (t, J = 6.8 Hz, 2H), 4.18 (t, J = 6.0 Hz, 2H), 2.70 (t, J = 7.8 Hz, 2H), 2.28 (p, J = 6.5 Hz, 2H), 1.73 - 1.62 (m, 2H), 1.42 (h, J = 7.4 Hz, 2H), 0.98 (t, J = 7.3 Hz, 3H).

Compound PLC-49 (9-(4-butylphenyl)-2-(3-(3,5-dichloro-4-(19,19-difluoro-6,7,11,12,13,19 -Hexahydro-5H-18l4,19l4-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- 𠮿 and[2,1,9-def]isoquinoline-1,3(2H)-dione): Compound PLC-49 was obtained 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 , then DDQ (0.157 mmol, 36 mg) and 2X Et ₃ N (0.738 mmol, 0.10 mL) and BF ₃ .OEt ₂ (1.107 mmol, 0.14 mL) in anhydrous DCM (20 mL) at room temperature, then in Synthesized at 50°C. The crude reaction mixture was loaded onto approximately 30 g of silica gel in the loader. Purified by flash chromatography on silica gel (120 g, solids load, equilibration 0% EtOAc/Hexane, eluting 0% (2 CV) to 5% EtOAc/DCM (30 CV)). Fractions containing product were evaporated to dryness in vacuo. Obtained 42 mg of dark red solid, 44% yield. MS ( _APCI ) _{: Calcd} for _Formula : _{C64H50BCl2F2N3O4} (M+H) = 1044; _found : 1044. ¹ H 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), 6.47 (s, 2H), 4.45 (s, 2H), 4.22 (t, J = 6.0 Hz, 6H), 2.70 (t, J = 7.8 Hz, 2H), 2.64 (t, J = 6.8 Hz, 4H), 2.42 - 2.23 (m, 6H), 2.11 - 1.97 (m, 4H), 1.73 – 1.62 (m, 2H), 1.42 (h, J = 7.3 Hz, 2H), 0.98 (t, J = 7.3 Hz, 3H).

Synthetic compound PLC-50 : Compound PLC-50.1 (2-(3-hydroxypropyl)-9-(4-(pentyloxy)phenyl)-1H-𠮿 and[2,1,9-def]isoquinoline-1,3(2H)-dione): Compound PLC-50.1 was self-contained in THF (30 mL)/DMF (6 mL) in a similar manner to the above procedure Compound PLC-38.1 (1.500 mmol, 636.0 mg), (4-(pentyloxy)phenyl)boronic acid (3.00 mmol, 624 mg), K ₂ CO ₃ (4.125 mmol, 570 mg)/water (3 mL) and Pd(dppf)Cl ₂ (0.105 mmol, 77 mg) were synthesized at 80°C. The precipitated compound was filtered off, washed with water, and dried in vacuo. Obtained as a tan solid, 730 mg (96% yield). MS (APCI): _{Calcd for Formula: C32H29NO5 (} M+H) = 508; _found : 508. ¹ H 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 = 6.1 Hz, 2H), 4.03 (t, J = 6.6 Hz, 2H), 3.62 - 3.51 (m, 2H), 3.25 (t , J = 6.9 Hz, 1H), 2.08 - 1.91 (m, 2H), 1.84 (p, J = 6.7 Hz, 2H), 1.55 - 1.34 (m, 4H), 0.97 (t, J = 7.1 Hz, 3H) .

Compound PLC-50.2 (4-methylbenzenesulfonic acid 3-(1,3-dioxo-9-(4-(pentyloxy)phenyl)-1H-𠮿 [2,1,9-def]isoquinolin-2(3H)-yl)propyl ester): Compound PLC -50.2 was obtained from compound PLC-50.2 contained in dry DCE (20 mL) in a similar manner to compound 46.2 50.1 (1.550 mmol, 787 mg), 4-methylbenzenesulfonic anhydride (6.202 mmol, 2024 mg) and Et ₃ N (6.977 mmol, 0.97 mL) were synthesized at 90°C. The crude product was loaded onto approximately 65 g of silica gel in the loader. Purified by flash chromatography on silica gel (120 g, solids load, equilibration 0% EtOAc/DCM, eluting 0% (2 CV) to 10% EtOAc/DCM (10 CV) to isocratic 10%). Fractions containing product were evaporated to dryness in vacuo to afford a yellow solid, 528 mg (51% yield). MS (APCI ₎ : _{Calcd. for Formula: C39H35NO7S (} M+H) = 662; found: 662. ¹ H 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 = 6.6 Hz, 2H), 2.42 (s, 3H), 2.12 ( p, J = 6.6 Hz, 2H), 1.90 - 1.77 (m, 2H), 1.55 - 1.34 (m, 4H), 0.97 (t, J = 7.1 Hz, 3H).

Compound PLC-50.3 (2,6-dichloro-4-(3-(1,3-dioxo-9-(4-(pentyloxy)phenyl)-1H-𠮿 and[2,1,9-def]isoquinolin-2(3H)-yl)propoxy)benzaldehyde): Compound PLC-50.3 was self-contained in anhydrous DMF (10 mL) in a similar manner to the above procedure The compound PLC-50.2 (0.180 mmol, 119 mg), 2,6-dichloro-4-hydroxybenzaldehyde (0.539 mmol, 103 mg) and K ₂ CO ₃ (0.503 mmol, 70 mg) was synthesized. The crude product was loaded onto about 15 g of silica gel in the loader. Purified by flash chromatography on silica gel (80 g, solids load, equilibration 0% EtOAc/DCM, eluting 0% (2 CV) to 15% EtOAc/DCM (10 CV)). Fractions containing product were evaporated to dryness in vacuo. Obtained as a yellow solid, 103 mg (84% yield). MS (APCI) _: Calcd. for Formula: _C39H31Cl2NO6 (M+H) = 680; _{found :} 680. ¹ H NMR (400 MHz, TCE) δ 10.37 (s, 1H), 8.62 (d, J = 7.9 Hz, 1H), 8.57 (d, J = 8.3 Hz, 1H), 8.20 (d, J = 2.2 Hz, 1H), 8.04 (d, J = 8.1 Hz, 1H), 7.65 - 7.58 (m, 2H), 7.46 (d, J = 8.6 Hz, 1H), 7.35 (d, J = 8.4 Hz, 1H), 7.08 - 7.02 (m, 2H), 6.85 (s, 2H), 4.38 (t, J = 6.8 Hz, 2H), 4.18 (t, J = 6.0 Hz, 2H), 4.03 (t, J = 6.6 Hz, 2H), 2.28 (p, J = 6.5 Hz, 2H), 1.84 (p, J = 6.7 Hz, 2H), 1.55 - 1.35 (m, 4H), 0.97 (t, J = 7.1 Hz, 3H).

Compound PLC-50 (2-(3-(3,5-dichloro-4-(19,19-difluoro-6,7,11,12,13,19-hexahydro-5H-18l4,19l4-benzene And[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-𠮿 and[2,1,9-def]isoquinoline-1,3(2H)-dione): Compound 48 was obtained 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, then DDQ (0.255 mmol, 58 mg) and 2X Et ₃ N (1.199 mmol, 0.17 mL) and BF ₃ .OEt ₂ (1.798 mmol, 0.22 mL) in anhydrous DCM (20 mL) at room temperature, then at 50 °C Synthesize. The crude reaction mixture was loaded onto approximately 30 g of silica gel in the loader. Purified by flash chromatography on silica gel (120 g, solids load, equilibrate and run 0% EtOAc/DCM isocratic). Fractions containing product were evaporated to dryness in vacuo. A dark red solid was obtained, 127 mg (79% yield). MS _{( APCI} ) _{: Calcd} for Formula: _{C65H52BCl2F2N3O5} (M+H) = ₁₀₇₄ ; found: 1074. ¹ H NMR (400 MHz, TCE) δ 8.67 (d, J = 7.9 Hz, 1H), 8.61 (d, J = 8.3 Hz, 1H), 8.20 (d, J = 2.2 Hz, 1H), 8.11 - 8.00 ( m, 3H), 7.74 (dd, J = 8.6, 2.1 Hz, 1H), 7.63 - 7.58 (m, 2H), 7.46 (d, J = 8.6 Hz, 1H), 7.41 - 7.33 (m, 5H), 7.33 - 7.26 (m, 2H), 7.04 (d, J = 8.9 Hz, 2H), 7.02 (s, 2H), 6.47 (s, 2H), 4.44 (t, J = 6.9 Hz, 2H), 4.22 (t, J = 6.0 Hz, 2H), 4.03 (t, J = 6.6 Hz, 2H), 2.64 (t, J = 6.7 Hz, 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).

Synthesis of compound PLC-51 : Compound PLC-51.1 (6-(2-amino-4-(tert-butyl)phenoxy)-2-(3-hydroxypropyl)-1H-benzo[de]isoquinoline-1,3 (2H)-diketone): Place a 100 mL 2N round bottom flask in an aluminum heating block and place a stir bar. The flask was fitted with a finned condenser/gas adapter and 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 mL of pure ethanol (20 mL ). The reaction was stirred under argon and the heating block was set to 95°C. The reaction mixture was stirred at this temperature for 2 hours, then cooled to room temperature. The reaction mixture was quenched with 6H HCl (3 mL) and diluted with water (ca. 100 mL). The resulting precipitate was filtered off and washed with water. The precipitate was dried in vacuo to afford a tan solid in quantitative yield. MS (APCI _{) : Calcd for Formula: C25H26N2O4 (} M+H) = 419; found: 419. ¹ H 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 - 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).

Compound PLC-51.2 (9-(tert-butyl)-2-(3-hydroxypropyl)-1H-𠮿 And[2,1,9-def]isoquinoline-1,3(2H)-dione): Add a stir bar to a 40 mL vial. To the vial was added NaNO2 (11.291 mmol, 779 mg) and water (4 mL). The vial was stirred in an ice-water bath at 0°C. A stir bar was also placed into a separate 40 mL vial. 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. An aqueous solution of _NaNO2 was added to the vial over a period of 10 minutes while stirring at 0 °C. The diazonium solution was stirred at 0 °C for 1 hour. At the same time, a 250 mL 2N round bottom flask was installed with a finned condenser, an addition funnel and a stirring bar. To the flask was added CuSO ₄ .5H ₂ O (10.237 mmol, 2.556 g) and water (35 mL). The solution was stirred at room temperature. The copper sulfate solution was heated to 130°C (heat block temperature) about 15 minutes before the one hour diazotization was terminated. The diazonium solution was transferred to the addition funnel and added to the reaction mixture over a period of about 15 minutes while stirring at high speed. The reaction mixture was stirred for an additional minute, then placed in a room temperature water bath. Once the reaction cooled to room temperature, the product was isolated by filtration. The crude product is a mixture of desired alcohol and acetate. 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 dissolved in DCM and evaporated onto silica gel in vacuo. Purified by flash chromatography on silica gel (120 g, solids load, equilibrate 0% EtOAc/DCM, elute 0% (2 CV) to 75% EtOAc/DCM (20 CV)). Fractions containing product were evaporated to dryness in vacuo. Obtained as a yellow solid, 379 mg (37% yield). MS (APCI): Calcd for Formula: _C25H23NO4 (M+H) = ₄₁₉ ; found _: 419. ¹ H NMR (400 MHz, TCE) δ 8.65 (d, J = 7.8 Hz, 1H), 8.60 (d, J = 8.4 Hz, 1H), 8.07 (d, J = 2.3 Hz, 1H), 8.01 (d, J = 8.0 Hz, 1H), 7.63 (dd, J = 8.7, 2.2 Hz, 1H), 7.37 (d, J = 8.7 Hz, 1H), 7.34 (d, J = 8.3 Hz, 1H), 4.33 (t, J = 6.1 Hz, 2H), 3.57 (q, J = 6.1 Hz, 2H), 3.26 (t, J = 6.9 Hz, 1H), 1.98 (p, J = 5.9 Hz, 2H), 1.44 (s, 9H) .

Compound PLC-51.3 (2-(3-bromopropyl)-9-(tert-butyl)-1H-𠮿 And [2,1,9-def]isoquinoline-1,3(2H)-dione): Place a 100 mL 2N round bottom flask in an aluminum heating block and place a stir bar. Install the flask with a finned condenser/gas adapter and flow control valve. The system was flushed with argon. To the flask was added PLC-51.2 (0.483 mmol, 194 mg) and carbon tetrabromide (0.725 mmol, 240 mg), followed by anhydrous 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 the loader. Purified by flash chromatography on silica gel (120 g, solids load, equilibrate 0% EtOAc/DCM, elute 0% (2 CV) to 10% EtOAc/DCM (20 CV)). Fractions containing product were evaporated to dryness in vacuo. Obtained as a yellow solid, 149 mg (66% yield). MS (APCI): _Calcd for Formula: _C25H22BrNO3 (M+H) = 464; _found : 464.

Compound PLC-51 (9-(tertiary butyl)-2-(3-(3,5-dichloro-4-(19,19-difluoro-6,7,11,12,13,19-hexa Hydrogen-5H-18l4,19l4-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-𠮿 and[2,1,9-def]isoquinoline-1,3(2H)-dione): Compound PLC-51 was obtained from compound PLC -51 contained in anhydrous DMF (10 mL) in a similar manner to the above procedure. 51.3 (0.391 mmol, 148 mg), 3,5-dichloro-4-(19,19-difluoro-6,7,11,12,13,19-hexahydro-5H-18l4,19l4-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 K ₂ CO ₃ (0.382 mmol, 53 mg )synthesis. 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 load, equilibration 0% EtOAc/DCM, elution 0% (2 CV ) to 5% EtOAc/DCM (50 CV)). Fractions containing product were evaporated to dryness in vacuo. A dark red solid was obtained, 153 mg (50% yield). MS ₍ APCI _{) : Calcd} . for Formula: _{C58H46BCl2F2N3O4} (M+H) = 968; found: ₉₆₈ . ¹ H NMR (400 MHz, TCE) δ 8.67 (d, J = 7.9 Hz, 1H), 8.60 (d, J = 8.3 Hz, 1H), 8.10 - 7.98 (m, 4H), 7.62 (dd, J = 8.8 , 2.2 Hz, 1H), 7.40 - 7.25 (m, 8H), 7.02 (s, 2H), 6.48 (s, 2H), 4.43 (t, J = 7.0 Hz, 2H), 4.21 (t, J = 6.0 Hz , 2H), 2.70 - 2.59 (m, 4H), 2.33 (t, J = 6.7 Hz, 6H), 2.12 - 1.98 (m, 4H), 1.44 (s, 9H).

Synthesis of compound PLC-52 : Compound PLC-52.1 (5,11-dibromo-1H,3H-iso[6,5,4-mna]𠮿 -1,3-diketone): Into a 2L 2N round bottom flask was placed a stir bar and fitted with a long-fin condenser. To this flask was added 1H,3H-iso[6,5,4-mna]𠮿 -1,3-Diketone ( Ex-1.3 , synthesized according to literature RSC Adv., 2014, 4, 53072-53078) (34.688 mmol, 10.00 g), followed by o-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 plugged and the reaction mixture was heated with an aluminum heating block at 75°C open to air over the weekend. The reaction mixture was cooled to room temperature and the solid was filtered off. The filtrate was diluted with hexane (about 20% by volume) and the second precipitate was filtered off. Both of these precipitates were dried in vacuo at 100°C. Orange solid, 10.866 g in total (69.9% yield). Both have similar LCMS and NMR. MS ( _APCI ) _: Calcd. for Formula: _Ci8H6Br2O4 (M+H) = 445; found _: 445. ¹ H NMR (400 MHz, TCE) δ 9.47 (dd, J = 8.4, 1.5 Hz, 1H), 8.76 (d, J = 14.2 Hz, 2H), 7.72 - 7.63 (m, 1H), 7.56 (dd, J = 8.3, 1.4 Hz, 1H), 7.46 (ddd, J = 8.5, 6.7, 1.9 Hz, 1H).

Compound PLC-52.2 (2-(4-(5,11-dibromo-1,3-dioxo-1H-𠮿 [2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid): compound PLC-52.2 was obtained from PLC contained in anhydrous DMF (65 mL) in a similar manner to the above procedure -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) were synthesized at 160°C. The crude reaction mixture was cooled to 0 °C and quenched with 6N HCl (about 5 mL) and diluted with water (up to about 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. Assuming 100% yield. MS (APCI): _Calcd for Formula: _C26H13Br2NO5 (M+H) = 578; _{found :} 578.

Compound PLC-52.3 (2-(4-(1,3-dioxo-5,11-bis(4-(trifluoromethyl)phenyl)-1H-𠮿 and[2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid): Compound PLC-52.3 is self-contained in THF (/60 mL), DMF (12 mL) and water ( 6 mL) of compound PLC-52.2 (3.500 mmol, 2.034 g), (4-(trifluoromethyl) phenyl) boronic acid (14.00 mmol, 2.659 g), K ₂ CO ₃ (19.25 mmol, 2.661 g) and Pd(dppf)Cl ₂ (0.0245 mmol, 179 mg) was synthesized by heating at 80°C overnight under argon atmosphere. The crude reaction mixture was evaporated to dryness in vacuo, dissolved in DCM, and evaporated in vacuo onto about 35 g of flash silica gel. Purified by flash chromatography on silica gel (220 g, equilibrated 0% EtOAc/DCM, eluting 0% (10 CV) to 15.3% EtOAc/DCM (15.3 CV) to 40% EtOAc/DCM (10 CV) to etc. Concentration 40% EtOAc/DCM). EtOAc contained 0.1% v/v TFA. Fractions containing product were evaporated to dryness in vacuo. A tan solid was obtained, 2.000 g (80.3% from compound 80.1 (1655-11)). MS (APCI): _Calcd . for Formula: _C40H21F6NO5 (M+H) = 710; found _: 710 _. ¹ H NMR (400 MHz, DMSO) δ 12.44 (s, 1H), 8.47 (s, 1H), 8.23 (s, 1H), 8.02 (d, J = 8.1 Hz, 2H), 7.97 - 7.88 (m, 4H ), 7.75 (d, J = 8.0 Hz, 2H), 7.49 - 7.37 (m, 3H), 7.31 (d, J = 8.2 Hz, 1H), 7.30 - 7.24 (m, 2H), 7.02 - 6.91 (m, 2H), 3.68 (s, 2H).

Compound PLC-52.4 : To a solution of compound PLC-29 (113 mg, 0.1 mmol) in 8 mL dry DCM and 3 mL 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 x 50 mL), loaded on silica gel and purified by flash chromatography using the eluent of DCM/EA (0% to 10% EA). Collect the main peak. After removal of the solvent and trituration with methanol, a reddish brown solid (80 mg, 58% yield) was obtained after filtration and drying in air. LCMS ( _APCI- ) _: Calcd _{. for C66H38BBr3Cl2F5N3O5} : _1364.98 ( _M- ); found: 1365.

Compound PLC-52.5 : 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) was degassed and heated at 80 °C for 6 hours. The resulting mixture was diluted with 100 mL of DCM, dry loaded on silica gel and purified by flash chromatography using the eluent of hexane/DCM (0% to 50% DCM). The first major peak was collected, and the solvent was removed to give the desired product (10 mg, 30% yield) as a red solid. LCMS ₍ APCI-): Calcd. _{for C53H49BCl2F2N2O : 848.33} (M-); found: 848. ¹ 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).

Compound PLC-52 : Compound PLC-52.5 (10 mg, 0.012 mmol), (2-(4-(1,3-dioxo-5,11-bis(4- (Trifluoromethyl)phenyl)-1H-𠮿 [2,1,9-def]isoquinolin-2(3H)-yl)phenyl)acetic acid) (16 mg, 0.022 mmol), DMAP/TsOH (5 mg, 0.017 mmol), DIC (0.05 mL, 0.31 mmol) was stirred overnight at room temperature. The resulting mixture was loaded on silica gel and purified by flash chromatography using the eluent of hexane/DCM (0% to 100% DCM). The main desired peak was collected to give a dark brown solid (10 mg, 54% yield) after solvent removal and trituration with MeOH. LCMS ₍ APCI- ₎ : _{Calcd .} for _{C93H68BCl2F8N3O5} : _1539.45 (M-); found: 1539. ¹ H 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 = 8.0 Hz, 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 = 7.4 Hz, 4H), 1.32 - 1.21 (m, 4H), 0.87 (t, J = 7.3 Hz, 6H).

Synthesis of compound PLC-53 Compound PLC-53.1 (9-(6-(2-amino-4-(tert-butyl)phenoxy)-2-(2-hydroxyethyl)-1H-benzo[de]isoquinoline- 1,3(2H)-diketone): Compound PLC-53.1 was obtained from 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 g of ethanol (70 mL). The crude precipitate was filtered off, dissolved in acetone, and evaporated to dryness in vacuo. A tan solid was obtained, 2.777 g (78% yield). MS (APCI): Calcd for C ₂₄ H ₂₄ N ₂ O ₄ (M+H) = 405; found: 405. ¹ H 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 - 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).

Compound PLC-53.2 (9-(tert-butyl)-2-(2-hydroxyethyl)-1H-𠮿 and[2,1,9-def]isoquinoline-1,3(2H)-dione): compound PLC-53.2 was obtained from compound PLC-53.1 (6.863 mmol, 2.776 g), NaNO ₂ (51.475 mmol, 3.552 g), concentrated HCl (34.317 mmol, 2.83 mL) and CuSO ₄ .5H ₂ O (46.67 mmol, 11.653 g). The crude product was about 10% acetate. It was cleaved using _K2CO3 in the same _manner as above. The crude cleavage mixture was dissolved in acetone and evaporated onto about 20 g of silica gel and placed in a loader. Purified by flash chromatography on silica gel (120 g, solids load, equilibrate 0% EtOAc/DCM, elute (2 CV) to 85% EtOAc/DCM (20 CV)). Fractions containing product were evaporated to dryness in vacuo. Obtained as a yellow solid, 732 mg (27% yield). MS (APCI): Calcd. for Formula: _C24H21NO4 (M+H) = ₃₈₈ ; found _: 388.

Compound PLC-53.3 (4-(2-(9-(tert-butyl)-1,3-two-side oxy-1H-𠮿 and[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) was added to a 40 mL screw cap vial, followed by anhydrous DCE (10 mL) and a stir bar. The reaction mixture was stirred at room temperature and DEAD (0.300 mmol, 0.137 mL) and _PPh3 (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 at room temperature overnight. The crude reaction mixture was loaded onto approximately 20 g of silica gel in the loader. Purified by flash chromatography on silica gel (80 g, solids load, equilibration 0% EtOAc/DCM, eluting 0% (2 CV) to 10% EtOAc/DCM (15 CV)). MS ₍ APCI) _: Calcd. for Formula: _C31H23Cl2NO5 (M+H) = 560; found _: 560. ¹ H NMR (400 MHz, TCE) δ 10.36 (s, 1H), 8.66 (d, J = 7.9 Hz, 1H), 8.60 (d, J = 8.5 Hz, 1H), 8.06 (d, J = 2.3 Hz, 1H), 8.01 (d, J = 8.0 Hz, 1H), 7.63 (dd, J = 8.7, 2.2 Hz, 1H), 7.37 (d, J = 8.8 Hz, 1H), 7.34 (d, J = 8.4 Hz, 1H), 6.99 (s, 2H), 6.95 (d, J = 14.5 Hz, 1H), 4.64 (t, J = 6.2 Hz, 2H), 4.39 (t, J = 6.2 Hz, 2H), 1.44 (s, 9H).

Compound PLC-53 (9-(tert-butyl)-2-(2-(4-(19,19-difluoro-6,7,11,12,13,19-hexahydro-5H-18l4,19l4 -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-𠮿 and[2,1,9-def]isoquinoline-1,3(2H)-dione): Compound PLC-53 was obtained 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.H ₂ O (0.0186 mmol, 3.5 mg), then DDQ (0.241 mmol, 55 mg) and 2X Et ₃ N (1.485 mmol, 0.210 mL) and BF ₃ .OEt ₂ (2.227 mmol, 0.280 mL) in anhydrous DCM (20 mL) at room temperature, then at 50°C Synthesize. The crude reaction mixture was diluted with hexanes and then loaded onto approximately 20 g of silica gel in a loader. Purified by flash chromatography on silica gel (80 g, solids load, equilibrate 0% EtOAc/hexane, elute 0% (2 CV) to 75% EtOAc/hexane (30 CV)). Fractions containing product were evaporated to dryness in vacuo. The crude product was triturated and dried in vacuo. A dark red solid was obtained, 138 mg (78% yield). MS _{(APCI): Calcd for Formula: C59H50BF2N3O4 ( M +} H) = 954; found: ₉₅₄ . ¹ H NMR (400 MHz, TCE) δ 8.70 (d, J = 7.9 Hz, 1H), 8.64 (d, J = 8.4 Hz, 1H), 8.10 - 7.99 (m, 4H), 7.63 (dd, J = 8.7 , 2.2 Hz, 1H), 7.42 - 7.32 (m, 6H), 7.32 - 7.24 (m, 2H), 7.14 (s, 2H), 6.43 (s, 2H), 4.70 (t, J = 6.2 Hz, 2H) , 4.42 (t, J = 6.3 Hz, 2H), 2.62 (t, J = 6.6 Hz, 4H), 2.30 (s, 4H), 2.11 - 1.96 (m, 4H), 1.44 (s, 9H).

Example 10 - Fabrication of Filter Layer A glass substrate was prepared in essentially the following manner. A 1.1 mm thick glass substrate measuring 1-inch by 1-inch was cut to size. The glass substrates were then washed with detergent and deionized (DI) water, rinsed with fresh DI water, and sonicated for about 1 hour. The glass was then immersed in isopropanol (IPA) and sonicated for about 1 hour. The glass substrate was then immersed in acetone and sonicated for about 1 hour. The glass was then removed from the acetone bath and dried with nitrogen at room temperature.

A 20 wt % solution of poly(methyl methacrylate) (PMMA) (average M.W. 120,000 by GPC, from MilliporeSigma, Burlington, MA, USA) copolymer in cyclopentanone (99.9% pure) was prepared. The prepared copolymer was stirred overnight at 40°C. [PMMA] CAS: 9011-14-7; [Cyclopentanone] CAS: 120-92-3.

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

A 1-inch by 1-inch sample was inserted into a Shimadzu, UV-3600 UV-VIS-NIR Spectrophotometer (Shimadzu Instruments, Inc., Columbia, MD, USA). All device manipulations were performed in a nitrogen-filled glove box. The resulting absorption/emission spectrum of PLC-1 is shown in FIG . 1 , that of PLC-2 is shown in FIG. 2 , and that of PLC-3 is shown in FIG. 3 .

Fluorescence spectra of 1-inch by 1-inch film samples prepared as described above were measured using a Fluorolog spectrophotometer (Horiba Scientific, Edison, NJ, USA) with excitation wavelengths set at the respective maximum absorption wavelengths. The maximum emission and FWHM are shown in Table 1.

Quantum yields of 1-inch by 1-inch samples prepared as described above were measured using a Quantarus-QY spectrophotometer (Hamamatsu Inc., Campbell CA, USA) excited at the respective maximum absorption wavelength. The results are reported in Table 1.

The results of film characteristic analysis (absorption peak wavelength, FWHM and quantum yield) are shown in Table 1 below. Table 1 Compound number structure Absorption in PMMA ( nm) Emission in PMMA ( nm) FWHM (nm) QY ( at 450 nm ) PLC-1 594 614 35 0.904 PLC-2 592 611 35 0.969 PLC-3 593 615 34 0.937 PLC-4 631 644 28 0.807 PLC-5 644 658 30 0.767 PLC-6 584 602 35 0.888 PLC-7 633 648 32 0.784 PLC-8 581 599 34 0.951 PLC-9 615 628 29 0.809 PLC-10 580 597 34 0.958 PLC-11 631 642 29 0.837 PLC-12 644 656 30 0.751 PLC-13 614 626 28 0.794 PLC-14 633 648 31 0.758 PLC-15 635 643 twenty four 0.862 PLC-16 593 612 36 0.85 PLC-17 644 658 30 0.701 PLC-18 585 602 34 0.873 PLC-19 644 658 30 0.735 PLC-20 593 612 35 0.820 PLC-21 616 626 25 0.861 PLC-22 582 600 37 0.917 PLC-23 592 610 34 0.912 PLC-24 593 615 34 0.924 PLC-25 593 614 34 0.912 PLC-26 593 610 33 0.887 PLC-27 593 611 34 0.894 PLC-28 593 611 33 0.897 PLC-29 592 608 32 0.889 PLC-30 593 611 34 0.907 PLC-31 593 612 35 0.895 PLC-32 593 612 34 0.859 PLC-33 593 612 34 0.909 PLC-34 591 609 33 0.892 PLC-35 591 608 33 0.915 PLC-36 593 612 34 0.909 PLC-37 592 608 33 0.890 PLC-38 591 607 33 0.867 PLC-39 593 610 33 0.903 PLC-40 591 608 34 0.85 PLC-41 591 605 32 0.898 PLC-42 592 610 34 0.869 PLC-43 591 608 34 0.869 PLC-44 592 609 34 0.911 PLC-45 592 612 33 0.877 PLC-46 592 608 33 0.842 PLC-47 592 610 33 0.885 PLC-48 592 612 33 0.864 PLC-49 591 607 36 0.867 PLC-50 591 607 35 0.859 PLC-51 591 606 34 0.857 PLC-52 592 611 35 0.86 PLC-53 592 608 33 0.84

CROSS REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Application No. 63/248,863, filed September 27, 2021, and U.S. Provisional Application No. 63/278,944, filed November 12, 2021, Both are incorporated by reference in their entirety.

Figure 1 is a graph depicting the absorption and emission spectra of one example of a photoluminescent complex (PLC-1).

Figure 2 is a graph depicting the absorption and emission spectra of one embodiment of the photoluminescent composite (PLC-2).

Figure 3 is a graph depicting the absorption and emission spectra of one embodiment of the photoluminescent composite (PLC-3).

Claims (17)

A photoluminescent compound comprising: a blue light absorbing donor chromophore, wherein the donor chromophore comprises a naphthyl imide derivative; linker complex; and ring-locked boron-dipyrromethane (BODIPY) moiety; Wherein the linker complex covalently connects the donor chromophore having the naphthyl imide derivative and the ring-locked BODIPY moiety, wherein the naphthyl imide derivative absorbs the blue light energy of the first excitation wavelength and transferring energy to the ring-locked BODIPY moiety, wherein the ring-locked BODIPY moiety emits light energy of a second, longer wavelength, and wherein the photoluminescent composite has an emission quantum yield of greater than 80%. The photoluminescent compound as claimed in item 1, wherein the naphthyl imide derivative of the donor chromophore has the following general formula: , wherein Y is O or S; wherein R ₇ and R ₈ are independently H, substituted or unsubstituted aryl, or -CF ₃ ; and wherein R ₉ is independently H, substituted or unsubstituted Aryl, or C ₁ -C ₅ alkyl. The photoluminescent compound as claimed in item 1, wherein the photoluminescent compound has the following general formula: , wherein R ₁ and R ₂ are independently H, C ₁ -C ₃ alkyl, or substituted aryl; wherein R ₃ and R ₄ are independently H, F, Br or -CF ₃ ; wherein R ₅ and R ₆ is independently H, C ₁ -C ₃ alkyl, halide, or C ₁ -C ₃ alkoxy; and wherein each X is independently C ₁ -C ₃ alkyl or spirocycloalkyl, wherein L is The linker complex and Z is the donor chromophore. The photoluminescent composite as claimed in item 3, wherein L is a substituted ester or an unsubstituted ester. The photoluminescent compound as claimed in item 3, wherein L is a substituted ether or an unsubstituted ether. The photoluminescent complex as claimed in claim 1, 3 or 4, wherein the linker complex is an unsubstituted ester; wherein the unsubstituted ester includes one of the following structures: The photoluminescent complex according to claim 1, 3 or 4, wherein the linker complex is a substituted ester; wherein the substituted ester includes one of the following structures: , or . The photoluminescent complex as claimed in item 1, 3 or 5, wherein the linker complex is an unsubstituted and/or substituted ether; wherein the unsubstituted and/or substituted ether includes one of the following structures one of: The photoluminescent composite according to claim 1, 3, 4 or 5, wherein the photoluminescent composite includes one of the following structures: (PLC-53) , or any combination thereof. A color conversion film comprising: Transparent substrate layer; A color conversion layer, wherein the color conversion layer comprises a resin matrix; and at least one photoluminescent compound according to claim 1, 2, 3, 4 or 5 dispersed in the resin matrix. The color conversion film according to claim 10, further comprising a singlet oxygen quencher. The color conversion film according to claim 10, further comprising a free radical scavenger. The color conversion film as claimed in item 10, wherein the film has a thickness between 10 µm and 200 µm. As claimed in item 10, the color conversion film, 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. A method of preparing a color conversion film, the method comprising: Dissolving the photoluminescent compound and binder resin according to claim 1, 2, 3, 4 or 5 in a solvent; and The mixture is applied to a transparent substrate layer. A backlight unit comprising the color conversion film according to Claim 10. A display device comprising the backlight unit according to claim 16.