TWI768777B - Boron-containing cyclic emissive compounds and color conversion film containing the same - Google Patents

Abstract

The present disclosure relates to novel photoluminescent complex comprising a BODIPY moiety covalently bonded to a blue light absorbing azole derivative, and a color conversion film, a backlight unit using the same.

Description

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

The present invention relates to compounds for use in color conversion films, backlight units, and display devices including the color conversion films and backlight units.

In color reproduction, a color gamut (gamut/color gamut) is a specific complete subset of colors available on a device (eg, 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 by a monitor, which is a wide color range achieved by using pure spectral primary colors gamut color space. It is believed that a device capable of providing a wider color gamut will allow the display to draw more vivid colors.

As high-definition large-screen displays become increasingly popular, so does the demand for higher-performance, thinner, and more powerful displays. Existing light emitting diodes (LEDs) are obtained by exciting green phosphors, red phosphors or yellow phosphors with a blue light source to obtain a white light source. However, the full width at half maximum (FWHM) of the emission peaks of existing green and red phosphors is large, typically greater than 40 nm, causing the green and red spectra to overlap and the colors to be indistinguishable from each other. Such overlap can result in poor color reproduction and gamut degradation.

In order to correct gamut degradation, the use of films containing quantum dots with A method of combining LEDs. However, there are problems with the use of quantum dots. First, cadmium-based quantum dots are extremely toxic and banned in many countries due to health and safety concerns. Second, non-cadmium-based quantum dots are very inefficient at converting blue LED light into green and red light. Third, quantum dots require expensive packaging processes to protect against moisture and oxygen. Finally, the cost of using quantum dots is high due to the difficulty in controlling dimensional uniformity during the production process.

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

Some embodiments include a photoluminescent complex comprising a blue light absorbing azole derivative; a linker group (such as a linker group comprising an unsubstituted or substituted ester); and two Boron Pyrrolomethylene (BODIPY) moiety. In some embodiments, the linker group can covalently link the azole derivative to the BODIPY moiety. In some embodiments, the azole derivative absorbs light at the first excitation wavelength and transfers energy to the BODIPY moiety. In some embodiments, the BODIPY moiety absorbs energy from the azole derivative and emits a second, higher wavelength optical energy. In some embodiments, the emission quantum yield of the photoluminescent complex is greater than 70%.

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

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

In some embodiments, the azole derivatives may have the following general formula:

In some embodiments, Z can be nitrogen (NR ¹⁰ ). In some embodiments, Z can be sulfur (S). In some embodiments, Z can be oxygen (O). In some embodiments, R ⁹ can be H or a linker (eg, an unsubstituted ester linker group or a substituted ester linker group). In some embodiments, R ¹⁰ can be H, a substituted aryl group, or a linker group (eg, an unsubstituted ester linker group or a substituted ester linker group).

其中R¹-R⁸如下面更詳細描述的，且L代表連接基基團，例如包含非取代之酯或經取代之酯的連接基基團。 In some embodiments, the BODIPY derivative can have the following general formula:

wherein R1 ^{- R8} are as described in more detail below, and L represents a linker group, eg, a linker group comprising an unsubstituted ester or a substituted ester.

Some embodiments include a color conversion film comprising: a color conversion layer, wherein the color conversion layer comprises a resin matrix; and a photoluminescent composite as described herein dispersed in the resin matrix Inside. In some embodiments, the thickness of the color conversion film may be between 1 μm and about 200 μm. In some embodiments, the color conversion film of the present invention can absorb blue light in the range of 400 nm to about 480 nm and emit light in the range of 510 nm to about 560 nm. Another embodiment describes a color conversion film that can absorb blue light in the range of 400 nm to about 480 nm and emit light in the wavelength range of 575 nm to about 645 nm. In some embodiments, the color conversion film may also include a transparent substrate layer. In some embodiments, the transparent substrate layer includes two opposing surfaces, wherein the color conversion layer is disposed on one of the opposing surfaces.

Some embodiments include a method of making the color conversion film, the method comprising: dissolving at least one of the photoluminescent composites described above and a binder resin in a solvent; and applying the mixture to one of opposing surfaces of a transparent substrate. on a surface.

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

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

Figure 2 is a graph depicting the absorption and emission spectra of one embodiment of the photoluminescent complex PLC-5.

Cross-references to related applications

This application claims the benefit of US Provisional Application No. 62/992,776, filed March 20, 2020, which is incorporated herein by reference in its entirety.

The present invention describes photoluminescent composites and the use of the photoluminescent composites in color conversion films. The photoluminescent composites can be used to improve and enhance the transmission of one or more desired emission bandwidths within the color conversion film. In some embodiments, the photoluminescent composite can simultaneously enhance transmission of a desired first emission bandwidth and reduce transmission of a second emission bandwidth. For example, color conversion films can enhance the contrast or intensity between two or more colors, thereby increasing the difference between them. The present invention describes photoluminescent composites that can enhance the contrast or intensity between two colors, thereby increasing their differentiation from each other.

As used herein, when a compound or chemical structure is referred to as being "substituted," it can contain one or more substituents. A substituted group is derived from an unsubstituted parent structure in which one or more hydrogen atoms on the parent structure have been independently replaced with one or more substituents. In one or more forms, substituents can be independently selected from optionally substituted alkyl, alkenyl, ketone, aryl, or C3 _{- C7} heteroalkyl.

The term "alkyl" group as used herein refers to a hydrocarbyl group without a C=C group or a C≡C group. An "alkenyl" moiety refers to a group having at least one carbon-carbon double bond (-C=C-), while an "alkynyl" moiety refers to a group having at least one carbon-carbon triple bond (-C≡C-). group. The alkyl, alkenyl or alkynyl moieties, whether saturated or unsaturated, may be branched, straight or cyclic.

The alkyl moiety can have 1 to 6 carbon atoms (whether or not it occurs herein, a numerical range such as "1 to 6" refers to each integer within the given range: eg, "1 to 6 carbon atoms" It is meant that an alkyl group can have 1 carbon atom, 2 carbon atoms, 3 carbon atoms, etc. up to and including 6 carbon atoms, but this definition also covers occurrences of the term "alkyl" without specifying a numerical range. The alkyl group of a compound of a can be referred to as a " _C1 - _C6 alkyl" or similar designation. By way of example only, " _C1 - _C6 alkyl" means the presence of one to six carbon atoms in the alkyl chain , that is, the alkyl chain is selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl. Therefore, C ₁ -C ₆ alkyl includes C ₁ -C ₂ alkyl, C ₁ -C ₃ alkyl, C ₁ -C ₄ alkyl, C ₁ -C ₅ alkyl. Alkyl groups can be substituted or unsubstituted. Typical alkyl groups Groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.

Typical alkenyl groups include vinyl, propenyl, butenyl, and the like.

The term "heteroalkyl," as used herein, refers to an alkyl group, as defined herein, in which one or more of the constituent carbon atoms in the alkyl group has been replaced with nitrogen, oxygen, or sulfur. Examples include, but are not limited to _-CH2 -O- _CH3 , _-CH2 - _CH2 -O- _CH3 , _-CH2 -NH- _CH3 , _-CH2 -N( _CH3 ) _-CH3 , -CH ₂ -CH ₂ -NH-CH ₃ , -CH ₂ -CH ₂ -N(CH ₃ )-CH ₃ , -CH ₂ -S-CH ₂ -CH ₃ , -CH ₂ -CH ₂ -S(O)- _CH3 . Additionally, up to two heteroatoms may be consecutive, such as, for example, _-CH2 -NH-O- _CH3 , and the like.

The term "aromatic" refers to a planar ring having a delocalized pi-electron system containing 4n+2 pi-electrons, where n is an integer. Aromatic rings can be formed from five, six, seven, eight, nine or more than nine atoms. Aromatics can be optionally substituted. The term "aromatic" includes 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.

、

、

、

等。多環基團之說明性示例包括以下部分：

[二環辛烷]、

[二環戊烷]、

[二環庚烷]、

[二環庚烷]、

[二環癸烷]、

[十氫化 萘]、

[八氫并環戊二烯]、

[八氫茚]、

[六氫茚]、

[1,2,3,4-四氫化萘]、

[2,3-二氫-1H- 茚]、

[1,1-二甲基-2,3-二氫-1H-茚]、

[2',3'- 二氫螺環[環戊烷-1,1'-茚]、或

[1,2,3,3a-四氫并環戊二烯]。 The term "hydrocarbon ring" refers to a monocyclic or polycyclic group containing only carbon and hydrogen and which may be saturated. Monocyclic hydrocarbon rings include groups having 3 to 12 carbon atoms. Illustrative examples of monocyclic groups include the following moieties:

,

,

,

Wait. Illustrative examples of polycyclic groups include the following moieties:

[bicyclooctane],

[dicyclopentane],

[bicycloheptane],

[bicycloheptane],

[Dicyclodecane],

[Decalin],

[Octahydrocyclopentadiene],

[octahydroindene],

[hexahydroindene],

[1,2,3,4-Tetrahydronaphthalene],

[2,3-dihydro- 1H -indene],

[1,1-Dimethyl-2,3-dihydro- 1H -indene],

[2',3'-dihydrospiro[cyclopentane-1,1'-indene], or

[1,2,3,3a-tetrahydrocyclopentadiene].

The term "aryl" as used herein refers to an aromatic ring wherein each atom forming the ring is a carbon atom. Aromatic rings can be formed from 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, phenanthryl, and the like.

The term "aralkyl" refers to a group as described herein substituted with an aryl group as defined herein Alkyl group as defined. Non-limiting aralkyl groups include benzyl, phenethyl; and the like.

The term "heteroaryl" refers to an aryl group containing one or more ring heteroatoms selected from nitrogen, oxygen and sulfur, wherein the heteroaryl group has 4 to 10 atoms in its ring system, which The limitation is that the ring of the group does not contain two adjacent oxygen or sulfur atoms. It should be understood that a heteroaromatic ring may have additional heteroatoms in the ring. In heteroaryl groups having two or more heteroatoms, the 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 backbone atoms of the ring is a nitrogen atom. Illustrative examples of heteroaryl groups include the following moieties: pyrrole, imidazole, pyridine, and the like.

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

The terms "bond", "bonded", "direct bond" or "single bond" as used herein refer to the connection between two atoms or between two atoms when the atoms connected by a bond are considered to be part of a larger structure. The chemical bond between the two parts.

The term "moiety" as used herein refers to a particular segment or functional group of a molecule. A chemical moiety is generally considered to be a chemical entity embedded in or attached to a molecule.

The term "cyano" or "nitrile" as used herein refers to any organic compound containing a -CN functional group.

The term "ester" refers to a chemical moiety having the formula -COOR, wherein R is selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl (bonded through a ring carbon), and heterocycle (bonded through a ring carbon) . Any hydroxyl or carboxyl side chain on the compounds described herein can be esterified. Any suitable method can be used to prepare such esters and can be readily found in known reference sources.

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

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

The term "azole" or "azole derivative" as used herein refers to a chemical moiety having the formula:

The term "BODIPY" as used herein refers to a chemical moiety having the formula:

The BODIPY moiety may consist of a dipyrromethene group complexed with a disubstituted boron atom (usually a BF ₂ unit). The IUPAC name for the BODIPY core is 4,4-difluoro-4-bora-3a,4a-diaza-s-dicyclopentadienacene (4,4-difluoro-4-bora-3a,4a- diaza-s-indacene).

Use of the terms "may" or "may be" should be interpreted as "is" or "is not", or alternatively "does" or "and" Short for "does not" or "will" or "will not". For example, the sentence "The blue light absorbing azole derivative can be separated from the BODIPY moiety by a distance of about 8 Å or more" should Explain, for example, "In some embodiments, the blue light absorbing azole derivative is separated from the BODIPY moiety by a distance of about 8 Å or more", or "In some embodiments, the blue light absorbing azole derivative is separated from the BODIPY moiety by a distance not about 8Å or greater".

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 complexes of the present invention comprise an absorbing luminescent moiety and an emitting luminescent moiety linked by a linker such that their distance is tuned for the absorbing luminescent moiety to transfer its energy to the acceptor for luminescence moiety, wherein then the acceptor emitting moiety is emitted at a second wavelength greater than the absorbed first wavelength.

The photoluminescent complex of the present invention comprises: a blue light absorbing azole derivative; a linking group; and a boron dipyrrole methylene (BODIPY) moiety. In some embodiments, the linker group can covalently link the azole derivative to the BODIPY moiety. In some embodiments, the azole derivative absorbs light at a first excitation wavelength and transfers energy to a BODIPY moiety, which then emits light energy at a second wavelength, wherein the second wavelength light energy is higher than the first wavelength wavelength. It is believed that energy transfer from the excited azole derivative to the BODIPY moiety occurs by Forster resonance energy transfer (FRET). The idea is that due to the absorption/emission spectrum of the photoluminescent complex, there are two main absorption bands in the absorption/emission spectrum, one at the blue absorption band (azole derivatives), one at the BODIPY absorption band, and Only one emission band is located 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 15%, greater than 20%, greater than 25%, greater than 30%, greater than 35%, greater than 40%, greater than 45%, greater than 50%, greater than 55%, greater than 60% , greater than 65%, greater than 70%, greater than 75%, greater than 80%, greater than 85%, greater than 90%, or greater than 95%; and/or up to 100%. The emission quantum yield can be determined by the photons that will be emitted Measured by dividing the number by the number of photons absorbed, the emission quantum yield is equivalent to the emission efficiency of the light-emitting portion. In some embodiments, the emission quantum yield of the absorbing light-emitting moiety may be greater than 80%. In some embodiments, the quantum yield may be greater than 0.8 (80%), 0.81 (81%), 0.82 (82%), 0.83 (83%), 0.84 (84%), 0.85 (85%), 0.86 (86 %), 0.87(87%), 0.88(88%), 0.89(89%), 0.9(90%), 0.91(91%), 0.92(92%), 0.93(93%), 0.94(94%) or 0.95 (95%); and/or up to 1 (100%). Measurement of quantum yield in films can be performed by a spectrophotometer, such as a Quantaurus-QY spectrophotometer (Humamatsu Corporation, Campbell, CA, USA).

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

In some embodiments, the Stokes shift of the photoluminescent composite can be equal to or greater than 45 nm. As used herein, the term "Stokes shift" refers to the distance between the excitation peak of the blue light absorbing moiety and the emission peak of the BODIPY moiety.

The photoluminescent complexes of the present invention may have tunable emission wavelengths. Different substitution patterns on the BODIPY moiety can tune the emission wavelength (eg, maximum emission wavelength or peak emission wavelength) to be between 510 nm and about 560 nm, or between about 610 nm and about 645 nm, or between such values Any wavelength within the bounds of any value.

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

In some embodiments, the photoluminescent complex can have an emission peak between 510 nm and 560 nm. In some embodiments, the emission peak may be between about 510 nm to about 515 nm, about 515 nm to about 520 nm, about 520 nm to about 525 nm, about 525 nm to about 530 nm, about 530 nm to about 535 nm, about 535 nm to about 540 nm, about 540 nm to about 545 nm, about 545 nm to about 550 nm, about 550 nm to about 555 nm, between about 555 nm to about 560 nm, or any wavelength within the range defined by any of these equivalents.

In another embodiment, the photoluminescent complex may have an emission peak between 610 nm and 645 nm. In some embodiments, the emission peak may be between 610 nm to about 615 nm, about 615 nm to about 620 nm, about 620 nm to about 625 nm, about 625 nm to about 630 nm, about 630 nm to about 635 nm, about 635 nm to about 640 nm, about 640 nm to about 645 nm, or any wavelength within the range bounded by any of these equivalents.

Other embodiments include photoluminescent complexes wherein the steric distance of the blue light absorbing azole derivative and the BODIPY moiety is adjusted by a linker group for transferring the energy of the blue light absorbing azole derivative to the BODIPY moiety.

The present invention describes a photoluminescent complex, wherein the photoluminescent complex may comprise a blue light absorbing azole derivative, a linking group and a BODIPY moiety. The linking group covalently links the blue light absorbing azole derivative to the BODIPY moiety. In some embodiments, the azole derivative absorbs light energy at a first excitation wavelength and transfers energy to the BODIPY moiety , wherein the BODIPY moiety absorbs the energy from the azole derivative and emits a second higher wavelength light energy. In some embodiments, the emission quantum yield of the photoluminescent complex is 70%-100%.

其中Z可選自NR¹⁰、S或O；R⁹為H或經取代之酯連接基；且R¹⁰為H、經取代之芳基、或經取代之酯連接基。 Some embodiments include blue light absorbing azole derivatives having the general formula:

wherein Z can be selected from ^NR10 , S, or O; ^R9 is H or a substituted ester linkage ^; and R10 is H, a substituted aryl, or a substituted ester linkage.

。在一些實施例中，R¹⁰為連接基基團，例如經取代之酯連接基基團。 In some embodiments, Z is S. In some embodiments, Z is O. In some embodiments, Z is NR ¹⁰ . In some embodiments, R ¹⁰ is H. In some embodiments, R ¹⁰ is substituted aryl. In some embodiments, R ¹⁰ is substituted phenyl. In some embodiments, R ¹⁰ is fluorophenyl, such as

. In some embodiments, R ¹⁰ is a linker group, eg, a substituted ester linker group.

In some embodiments, the azole derivative can be a compound wherein Z can be NR ¹⁰ , R ⁹ can be H, and R ¹⁰ can be an unsubstituted ester linking group.

In some embodiments, the azole derivative can be a compound wherein Z can be NR ¹⁰ , R ⁹ can be H, and R ¹⁰ can be a substituted ester linking group.

In some embodiments, the azole derivative can be a compound wherein Z can be NR ¹⁰ , R ⁹ can be an unsubstituted ester linker, and R ¹⁰ can be a substituted aryl group.

In some embodiments, the azole derivative can be a compound wherein Z can be S and R ⁹ can be a substituted ester linker.

。 In some embodiments, wherein Z is NR ¹⁰ and R ¹⁰ is a substituted aryl group, wherein the substituted aryl group can be selected from the following structures:

.

The linking group covalently links the blue light absorbing azole derivative to the BODIPY moiety. The linking group can be varied to adjust the steric distance between the blue light absorbing azole derivative and the BODIPY moiety. By adjusting the spatial distance between the azole derivative and the BODIPY, the quantum yield can be tuned.

In some embodiments, L may represent a linker group.

The linker group, eg, L, can include a substituted ester linker group. The substituted ester linker may comprise one of the following structures:

Alternatively, the linker group, such as L, may comprise an unsubstituted ester linker group. The unsubstituted ester linkage can comprise one of the following structures:

R¹可為H、烷基、烯基、炔基或烷氧基-3-氧丙烯-1-基。在一些實施例中，R¹為H。在一些實施例中，R¹為烷基，例如C_1-6烷基(例如甲基、乙基、丙基、異丙基、C₄烷基、C₅烷基或C₆烷基)。在一些實施例中，R¹為烯基，例如C_2-6烯基(例如乙烯基、丙烯基、C₄烯基、C₅烯基、C₆烯基)。在一些實施例中，R¹為炔基，例如C_2-6炔基(例如乙炔基、丙炔基、C₄炔基、C₅炔基、C₆炔基)。在一些實施例中，R¹為烷氧基-3-氧丙烯-1-基，例如，

；在一些實施例中，R¹為甲氧基-3-氧丙烯-1-基，例如，

；在一些實施例中，R¹為乙氧基-3-氧丙烯-1-基，例如，

；在一些實施例中，R¹為丙氧基-3-氧丙烯-1-基。對於R¹的烷氧基-3-氧-丙烯-1-基酯，亦設想了其他烷氧基基團。R⁶可為H、烷基、烯基、炔基或烷氧基-3-氧丙烯-1-基。在一些實施例中，R⁶為H。在一些實施例中，R⁶為烷基，例如C_1-6烷基(例如甲基、乙基、丙基、異丙基、C₄烷基、C₅烷基或C₆烷基)。在一些實施例中，R⁶為烯基，例如C_2-6烯基(例如乙烯基、丙烯基、C₄烯基、C₅烯基、C₆烯基)。在一些實施例中，R⁶為炔基，例如C_2-6炔基(例如乙炔基、丙炔 基、C₄炔基、C₅炔基、C₆炔基)。在一些實施例中，R⁶為烷氧基-3-氧丙烯-1-基，例如甲氧基-3-氧丙烯-1-基、乙氧基-3-氧丙烯-1-基、丙氧基-3-氧丙烯-1-基等。在一些實施例中，R⁶為乙氧基-3-氧丙烯-1-基。 The photoluminescent composites of the present invention may contain a BODIPY moiety. The BODIPY moiety may have the following general formula:

R1 can be H, alkyl, alkenyl, alkynyl or alkoxy-3-oxopropen- ¹ -yl. In some embodiments, R ¹ is H. In some embodiments, R ¹ is alkyl, such as C _1-6 alkyl (eg, methyl, ethyl, propyl, isopropyl, C ₄ alkyl, C ₅ alkyl, or C ₆ alkyl). In some embodiments, R ¹ is alkenyl, eg, C _2-6 alkenyl (eg, vinyl, propenyl, C ₄ alkenyl, C ₅ alkenyl, C ₆ alkenyl). In some embodiments, R ¹ is an alkynyl group, such as a C _2-6 alkynyl group (eg, ethynyl, propynyl, C ₄ alkynyl, C ₅ alkynyl, C ₆ alkynyl). In some embodiments, R ¹ is alkoxy-3-oxopropen-1-yl, eg,

; In some embodiments, R ¹ is methoxy-3-oxopropen-1-yl, for example,

; In some embodiments, R ¹ is ethoxy-3-oxypropen-1-yl, for example,

; In some embodiments, R ¹ is propoxy-3-oxopropen-1-yl. Other alkoxy groups are also contemplated for the alkoxy-3-oxo-propen-1-yl ester of R ¹ . R ⁶ can be H, alkyl, alkenyl, alkynyl or alkoxy-3-oxopropen-1-yl. In some embodiments, R ⁶ is H. In some embodiments, R ⁶ is alkyl, such as C _1-6 alkyl (eg, methyl, ethyl, propyl, isopropyl, C ₄ alkyl, C ₅ alkyl, or C ₆ alkyl). In some embodiments, R ⁶ is alkenyl, eg, C _2-6 alkenyl (eg, vinyl, propenyl, C ₄ alkenyl, C ₅ alkenyl, C ₆ alkenyl). In some embodiments, R ⁶ is alkynyl, such as C _2-6 alkynyl (eg, ethynyl, propynyl, C ₄ alkynyl, C ₅ alkynyl, C ₆ alkynyl). In some embodiments, R ⁶ is alkoxy-3-oxopropen-1-yl, eg, methoxy-3-oxopropen-1-yl, ethoxy-3-oxopropen-1-yl, propyl Oxy-3-oxopropen-1-yl, etc. In some embodiments, R ⁶ is ethoxy-3-oxopropen-1-yl.

R ³ can be H or alkyl, such as C _1-6 alkyl or C ₁ -C ₂ alkyl. In some embodiments, R ³ is H. In some embodiments, R ³ is C ₁ -C ₂ alkyl. In some embodiments, R ³ is methyl.

R ⁴ can be H or alkyl, such as C _1-6 alkyl or C ₁ -C ₂ alkyl. In some embodiments, R ⁴ is H. In some embodiments, R ⁴ is C ₁ -C ₂ alkyl. In some embodiments, R ⁴ is methyl.

R2 can be H, alkyl, alkenyl, alkynyl, -CN, alkyl esters (eg, _-C (O) ^OCH2CH3 ₎ or aryl esters (eg, _-COOCH2Ar ). In some embodiments, R ² is H. In some embodiments, R ² is alkyl, such as C _1-6 alkyl (eg, methyl, ethyl, propyl, isopropyl, C ₄ alkyl, C ₅ alkyl, or C ₆ alkyl). In some embodiments, R ² is alkenyl, eg, C _2-6 alkenyl (eg, vinyl, propenyl, C ₄ alkenyl, C ₅ alkenyl, C ₆ alkenyl). In some embodiments, R ² is alkynyl, eg, C _2-6 alkynyl (eg, ethynyl, propynyl, C ₄ alkynyl, C ₅ alkynyl, C ₆ alkynyl). In some embodiments, R ² is -CN. In some embodiments, R ² is an alkyl ester (eg, -C(O)OCH ₂ CH ₃ ). In some embodiments, R ² is an aryl ester (eg, -COOCH ₂ Ar).

^R5 can be H, alkyl, alkenyl, alkynyl, -CN, an alkyl ester (eg, -C(O) _{OCH2CH3 )} , or an aryl ester (eg, _-COOCH2Ar ). ^In some embodiments, R5 is H. In some embodiments, R ⁵ is alkyl, such as C _1-6 alkyl (eg, methyl, ethyl, propyl, isopropyl, C ₄ alkyl, C ₅ alkyl, or C ₆ alkyl). In some embodiments, R ⁵ is alkenyl, eg, C _2-6 alkenyl (eg, vinyl, propenyl, C ₄ alkenyl, C ₅ alkenyl, C ₆ alkenyl). In some embodiments, R ⁵ is alkynyl, eg, C _2-6 alkynyl (eg, ethynyl, propynyl, C ₄ alkynyl, C ₅ alkynyl, C ₆ alkynyl). In some embodiments, R ⁵ is -CN. In some embodiments, R ⁵ is an alkyl ester (eg, -C(O)OCH ₂ CH ₃ ). In some embodiments, R ⁵ is an aryl ester (eg, -COOCH ₂ Ar).

R ² and R ³ can be joined together to form additional monocyclic hydrocarbon ring structures or polycyclic hydrocarbon ring structures; R ⁴ and R ⁵ can be joined together to form additional monocyclic hydrocarbon ring structures or polycyclic hydrocarbon ring structures; R ⁷ can be H or an alkyl group, such as a C _1-6 alkyl group (eg, methyl, ethyl, propyl, isopropyl, C ₄ alkyl, C ₅ alkyl, or C ₆ alkyl). In some embodiments, ^R7 is H. In some embodiments, R ⁷ is methyl (-CH ₃ ).

^R8 can be H or alkyl, such as _C1-6 alkyl (eg, methyl, ethyl, propyl, isopropyl, _C4 alkyl, _C5 alkyl, or _C6 alkyl). In some embodiments, ^R8 is H. In some embodiments, R ⁸ is methyl (-CH ₃ ).

L is a linker group, such as a substituted ester linker group.

In some embodiments, both R ⁷ and R ⁸ are methyl.

In some embodiments, R ¹ , R ³ , R ⁴ , and R ⁶ are all C ₁ -C ₂ alkyl groups.

In some embodiments, R ¹ , R ³ , R ⁴ and R ⁶ are all methyl.

In some embodiments, R ¹ and R ⁶ are both:

In some examples, a BODIPY moiety of the present invention can be a BODIPY moiety wherein R ¹ , R ³ , R ⁴ and R ⁶ are each methyl; R ² and R ⁵ are both cyano groups; R ⁷ and R ⁸ each is methyl; and L contains a linking group.

In some embodiments, the BODIPY moiety of the present invention may be a BODIPY moiety wherein R ¹ , R ³ , R ⁴ and R ⁶ are each methyl; R ² and R ⁵ are both substituted ester groups, wherein the The substituted ester group contains an alkyl chain; ^R7 and ^R8 are each methyl; and L contains a linking group.

In other embodiments, the BODIPY moiety of the present invention may be the following BODIPY moiety, wherein R ¹ , R ³ , R ⁴ and R ⁶ are each methyl; R ² and R ⁵ are both aryl ester groups; R ⁷ and R ⁸ are all methyl groups; and L includes a linking group.

^In some embodiments, BODIPY moieties of the present invention can include ^BODIPY moieties wherein R and R can be alkenyl, R and ^R are linked together to form ^a monocyclic hydrocarbon ring structure, and ^R and R ^are linked together to form a monocyclic hydrocarbon ring structure, and ^R7 and ^R8 can be H or methyl.

^In some embodiments, BODIPY moieties of the present invention can include ^BODIPY moieties wherein R and R can be alkenyl, R and ^R are linked together to form ^a polycyclic hydrocarbon ring structure, and ^R and R ^are linked together to form a polycyclic hydrocarbon ring structure, and ^R7 and ^R8 can be H or methyl.

。 In some embodiments, R ² and R ⁵ can be substituted esters, wherein the substituted esters are aryl esters. The aryl ester can have the following structure:

.

。 In some embodiments, R ² and R ⁵ can be substituted esters, wherein the substituted esters are alkyl esters. The alkyl ester can have the following structure:

.

。 In some embodiments, R ¹ and R ⁶ can be substituted alkenyl groups. The substituted alkenyl group can have the following structure:

.

[環丁烷]、

[環戊 烷]、

[環己烷]、

[環庚烷]、

[環辛烷]、

[環己 烯]、

[環己-1,4二烯]、

[環戊烯]、

[環己-1,3二烯]、 或

[環十二烷]。在一些實施例中，在R²及R³連接在一起以形成多 環烴環結構之情況下，該結構可選自以下：

[二環辛烷]、

[二環戊烷]、

[二環庚烷]、

{二環[4.1.0]庚 烷]、

[1s,5s二環[3.3.1]壬烷]、

[十氫化萘]、

[八氫并環戊二烯]、

[八氫茚]、

[六 氫茚]、

[1,2,3,4-四氫化萘]、

[2,3-二氫-1H- 茚]、

[1,1-二甲基-2,3-二氫-1H-茚]、

[2',3'- 二氫螺環[環戊烷-1,1'-茚]、或

[1,2,3,3a-四氫并環戊二烯]。 In some embodiments, R ² and R ³ may be linked together to form additional monocyclic hydrocarbon ring structures or polycyclic hydrocarbon ring structures. ^In embodiments, where R and R are linked together to form ^a monocyclic hydrocarbon ring structure, the structure may be selected from the following:

[cyclobutane],

[cyclopentane],

[cyclohexane],

[cycloheptane],

[cyclooctane],

[cyclohexene],

[Cyclohex-1,4-diene],

[cyclopentene],

[Cyclohex-1,3-diene], or

[cyclododecane]. ^In some embodiments, where R and ^R are linked together to form a polycyclic hydrocarbon ring structure, the structure can be selected from the following:

[bicyclooctane],

[dicyclopentane],

[bicycloheptane],

{bicyclo[4.1.0]heptane],

[1s,5sbicyclo[3.3.1]nonane],

[Decalin],

[Octahydrocyclopentadiene],

[octahydroindene],

[hexahydroindene],

[1,2,3,4-Tetrahydronaphthalene],

[2,3-dihydro- 1H -indene],

[1,1-Dimethyl-2,3-dihydro- 1H -indene],

[2',3'-dihydrospiro[cyclopentane-1,1'-indene], or

[1,2,3,3a-tetrahydrocyclopentadiene].

[環丁烷]、

[環戊 烷]、

[環己烷]、

[環庚烷]、

[環辛烷]、

[環己 烯]、

[環己-1,4二烯]、

[環戊烯]、

[環己-1,3二烯]、 或

[環十二烷]。在一些實施例中，在R⁴及R⁵連接在一起以形成多環烴環結構之情況下，該結構可選自以下：

[二環辛烷]、

[二環戊烷]、

[二環庚烷]、

[二環[4.1.0]庚 烷]、

[1s,5s二環[3.3.1]壬烷]、

[十氫化萘]、

[八氫并環戊二烯]、

[八氫茚]、

[六 氫茚]、

[1,2,3,4-四氫化萘]、

[2,3-二氫-1H- 茚]、

[1,1-二甲基-2,3-二氫-1H-茚]、

[2',3'-二氫螺環[環戊烷-1,1'-茚]、或

[1,2,3,3a-四氫并環戊二烯]。 ^In some embodiments, R4 and ^R5 can be linked together to form additional monocyclic hydrocarbon ring structures or polycyclic hydrocarbon ring structures. ^In embodiments, where R and R ^are linked together to form a monocyclic hydrocarbon ring structure, the structure may be selected from the following:

[cyclobutane],

[cyclopentane],

[cyclohexane],

[cycloheptane],

[cyclooctane],

[cyclohexene],

[Cyclohex-1,4-diene],

[cyclopentene],

[Cyclohex-1,3-diene], or

[cyclododecane]. ^In some embodiments, where R and R ^are linked together to form a polycyclic hydrocarbon ring structure, the structure can be selected from the following:

[bicyclooctane],

[dicyclopentane],

[bicycloheptane],

[bicyclo[4.1.0]heptane],

[1s,5sbicyclo[3.3.1]nonane],

[Decalin],

[Octahydrocyclopentadiene],

[octahydroindene],

[hexahydroindene],

[1,2,3,4-Tetrahydronaphthalene],

[2,3-dihydro- 1H -indene],

[1,1-Dimethyl-2,3-dihydro- 1H -indene],

[2',3'-dihydrospiro[cyclopentane-1,1'-indene], or

[1,2,3,3a-tetrahydrocyclopentadiene].

其中R¹及R²可連接在一起以形成另外的單環烴環結構或多環烴環結構；R³及R⁴可為H；R⁵及R⁶可連接在一起以形成另外的單環烴環結構或多環烴環結構；R⁷及R⁸獨立地選自H、甲基或醚基；及L代表連接基基團，該連接基基團包括經取代之酯連接基基團。 The photoluminescent complex may comprise a BODIPY moiety having the formula:

wherein R ¹ and R ² can be joined together to form additional monocyclic hydrocarbon ring structures or polycyclic hydrocarbon ring structures; R ³ and R ⁴ can be H; R ⁵ and R ⁶ can be joined together to form additional monocyclic rings A hydrocarbon ring structure or a polycyclic hydrocarbon ring structure; R ⁷ and R ⁸ are independently selected from H, methyl or ether groups; and L represents a linker group including a substituted ester linker group.

In some embodiments, R ¹ and R ² can be linked together to form a polycyclic hydrocarbon ring structure; R ³ and R ⁴ are both methyl; R ⁵ and R ⁶ can be linked together to form a polycyclic hydrocarbon ring structure; R ⁷ and R ⁸ can be selected from H, methyl or ether groups; and L is a linking group.

[環丁烷]、

[環戊 烷]、

[環己烷]、

[環庚烷]、

[環辛烷]、

[環己 烯]、

[環己-1,4二烯]、

[環戊烯]、

[環己-1,3二烯]、 或

[環十二烷]。在一些實施例中，在R¹及R²連接在一起以形成多環烴環結構之情況下，該結構可選自以下：

[二環辛烷]、

[二環戊烷]、

[二環庚烷]、

{二環[4.1.0]庚烷]、

[1s,5s二環[3.3.1]壬烷]、

[十氫化萘]、

[八氫并環戊二烯]、

[八氫茚]、

[六 氫茚]、

[1,2,3,4-四氫化萘]、

[2,3-二氫-1H- 茚]、

[1,1-二甲基-2,3-二氫-1H-茚]、

[2',3'- 二氫螺環[環戊烷-1,1'-茚]、或

[1,2,3,3a-四氫并環戊二烯]。 In some embodiments, R ¹ and R ² can be linked together to form additional monocyclic hydrocarbon ring structures or polycyclic hydrocarbon ring structures. ^In embodiments, where R and R are linked together to form ^a monocyclic hydrocarbon ring structure, the structure may be selected from the following:

[cyclobutane],

[cyclopentane],

[cyclohexane],

[cycloheptane],

[cyclooctane],

[cyclohexene],

[Cyclohex-1,4-diene],

[cyclopentene],

[Cyclohex-1,3-diene], or

[cyclododecane]. ^In some embodiments, where R and R are linked together to form ^a polycyclic hydrocarbon ring structure, the structure can be selected from the following:

[bicyclooctane],

[dicyclopentane],

[bicycloheptane],

{bicyclo[4.1.0]heptane],

[1s,5sbicyclo[3.3.1]nonane],

[Decalin],

[Octahydrocyclopentadiene],

[octahydroindene],

[hexahydroindene],

[1,2,3,4-Tetrahydronaphthalene],

[2,3-dihydro- 1H -indene],

[1,1-Dimethyl-2,3-dihydro- 1H -indene],

[2',3'-dihydrospiro[cyclopentane-1,1'-indene], or

[1,2,3,3a-tetrahydrocyclopentadiene].

[環丁烷]、

[環戊 烷]、

[環己烷]、

[環庚烷]、

[環辛烷]、

[環己 烯]、

[環己-1,4二烯]、

[環戊烯]、

[環己-1,3二烯]、 或

[環十二烷]。在一些實施例中，在R⁵及R⁶連接在一起以形成多 環烴環結構之情況下，該結構可選自以下：

[二環辛烷]、

[二環戊烷]、

[二環庚烷]、

{二環[4.1.0]庚 烷]、

[1s,5s二環[3.3.1]壬烷]、

[十氫化萘]、

[八氫并環戊二烯]、

[八氫茚]、

[六 氫茚]、

[1,2,3,4-四氫化萘]、

[2,3-二氫-1H- 茚]、

[1,1-二甲基-2,3-二氫-1H-茚]、

[2',3'- 二氫螺環[環戊烷-1,1'-茚]、或

[1,2,3,3a-四氫并環戊二烯]。 In some embodiments, R ⁵ and R ⁶ may be linked together to form additional monocyclic hydrocarbon ring structures or polycyclic hydrocarbon ring structures. ^In embodiments, where R and R ^are linked together to form a monocyclic hydrocarbon ring structure, the structure may be selected from the following:

[cyclobutane],

[cyclopentane],

[cyclohexane],

[cycloheptane],

[cyclooctane],

[cyclohexene],

[Cyclohex-1,4-diene],

[cyclopentene],

[Cyclohex-1,3-diene], or

[cyclododecane]. ^In some embodiments, where R and R ^are linked together to form a polycyclic hydrocarbon ring structure, the structure can be selected from the following:

[bicyclooctane],

[dicyclopentane],

[bicycloheptane],

{bicyclo[4.1.0]heptane],

[1s,5sbicyclo[3.3.1]nonane],

[Decalin],

[Octahydrocyclopentadiene],

[octahydroindene],

[hexahydroindene],

[1,2,3,4-Tetrahydronaphthalene],

[2,3-dihydro- 1H -indene],

[1,1-Dimethyl-2,3-dihydro- 1H -indene],

[2',3'-dihydrospiro[cyclopentane-1,1'-indene], or

[1,2,3,3a-tetrahydrocyclopentadiene].

In some embodiments, the blue light absorbing azole derivative can be separated from the BODIPY moiety by a distance of about 8 Å or more. The linking group maintains the distance between the blue light absorbing azole derivative and the BODIPY moiety.

In some embodiments, the photoluminescent complex comprises a linker group, wherein the linker group covalently links the blue light absorbing azole derivative to the BODIPY moiety. In some embodiments, the linker group may comprise a single bond between the azole derivative and the BODIPY moiety.

In some embodiments, the linker group may comprise an optionally substituted C2 _{- C16} ester group. When the linker group comprises a substituted ester group, the linker group may be:

In some embodiments, the linking group may comprise an unsubstituted ester group. When the linker group comprises an unsubstituted ester group, the linker group may be:

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

。 and/or

.

In some embodiments, the photoluminescent complex comprises a blue light absorbing azole derivative. The blue light absorbing azole derivative may contain an organic luminophore. In some embodiments, the azole derivatives can react at 400 nm to about 480 nm, about 400 nm to about 410 nm, about 410 nm to about 420 nm, about 420 nm to about 430 nm, about 430 nm to about 440 nm, about 440 nm to about 450 nm, about Light has a maximum absorbance at any wavelength in the range of 450 nm to about 460 nm, about 460 nm to about 470 nm, about 470 nm to about 480 nm, or within the range defined by any of these values. In some embodiments, the photoluminescent complex may have an absorbance maximum peak at about 450 nm. In other embodiments, the blue light absorbing azole derivative can have a maximum peak absorbance at about 405 nm. In other embodiments, the blue light absorbing azole derivative can have a maximum peak absorbance at about 480 nm.

Some embodiments include a color conversion film comprising: a color conversion layer comprising a resin matrix; and the above-described photoluminescent composite, the photoluminescent The luminescent complex is dispersed within the resin matrix. In some embodiments, a color conversion film can be described as comprising a combination of the compounds described herein.

Some embodiments include color conversion films that can be about 1 μm to about 200 μm thick. In some embodiments, the thickness of the color conversion film is about 1 μm to about 2 μm, about 2-3 μm, about 3-4 μm, about 4-5 μm, about 5-6 μm, about 6-7 μm, about 7-8 μm, about 8-9μm, about 9-10μm, about 1-5μm, about 5-10μm, about 10-15μm, about 15-20μm, about 20-40μm, about 40-80μm, about 80-120μm, about 120-160μm, about 160-200 μm, or any thickness within the range defined by any of these values.

In some embodiments, the color conversion film can absorb light in the wavelength range of 400 nm to about 480 nm, and can emit light in the range of about 510 nm to about 560 nm or about 610 nm to about 645 nm. In other embodiments, the color converting film may emit light in the range of 510 nm to about 560 nm, 610 nm to about 645 nm, or any combination thereof.

In some embodiments, the color conversion film may also 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 surfaces of the transparent layer that will be adjacent to the light emitting source. The transparent substrate is not particularly limited, and one skilled in the art will be able to select a transparent substrate from among 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 (ethylene glycol modified polyethylene terephthalate) Ethylene glycol formate), PDMS (polydimethylsiloxane), COC (cyclic olefin copolymer), PGA (polyglycolide or polyglycolic acid), PLA (polylactic acid), PCL (polycaprolactone) ), PEA (polyethylene adipate), PHA (polyhydroxyalkanoate), PHBV (poly(3-hydroxybutyrate-co-3-hydroxyvalerate)), PBE (polybutylene terephthalate), PTT (polytrimethylene terephthalate), etc.

In some embodiments, the transparent substrate may have two opposing surfaces. In some embodiments, a color conversion film may be disposed on and in physical contact with one of the opposing surfaces. In some embodiments, the side of the transparent substrate on which the color conversion film is not disposed may be adjacent to the light source. The substrate can be used as a support during the production of the color conversion film. There is no particular limitation on the type of substrate used, and there is no limitation on the material and/or thickness, as long as the substrate is transparent and capable of serving as a support. One skilled in the art can determine which material and thickness to use as the support substrate.

Some embodiments include a method for making a color conversion film, wherein the method comprises: 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 include, for example, the following resins: acrylic resins, polycarbonate resins, ethylene-vinyl alcohol copolymer resins, ethylene-vinyl acetate copolymer resins and their saponification products, AS resins, Polyester resins, vinyl chloride-vinyl acetate copolymer resins, polyvinyl butyral resins, polyvinylphosphonic acid (PVPA), polystyrene resins, phenolic resins, phenoxy resins, polysilicon, nylon, fibers Plain resin and cellulose acetate resin. In some embodiments, the binder resin may be polyester resin and/or acrylic resin.

烷及四氫呋喃；酯，例如乙酸丁酯、乙酸戊酯、丁酸乙酯、丁酸丁酯、草酸二乙酯、丙酮酸乙酯、2-羥基丁酸乙酯、乙醯乙酸乙酯、乳酸甲酯、乳酸乙酯及3-甲氧基丙酸甲酯；鹵代烴，例如氯仿、二氯甲烷及四氯乙烷；芳香烴，例如苯、甲苯、二甲苯及甲酚；以及高極性溶劑，例如二甲基甲醯胺、二甲基乙醯胺及N-甲基吡咯啶酮。 Solvents that can be used to dissolve or disperse the composites and resins 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, decanol, undecanol, diacetone alcohol and furfuryl 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, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetic acid Esters, 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 dipropylene

Alkane and tetrahydrofuran; esters such as butyl acetate, pentyl acetate, ethyl butyrate, butyl butyrate, diethyl oxalate, ethyl pyruvate, ethyl 2-hydroxybutyrate, ethyl acetoacetate, lactic acid Methyl ester, ethyl lactate, and methyl 3-methoxypropionate; halogenated hydrocarbons such as chloroform, dichloromethane, and tetrachloroethane; aromatic hydrocarbons such as benzene, toluene, xylene, and cresol; and highly polar Solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone.

Some embodiments include a backlight unit, wherein the backlight unit can include the color conversion film described above.

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

Unless otherwise stated, all numbers used in the specification and examples indicating amounts, properties (such as molecular weights) of ingredients, reaction conditions, etc., are to be understood as being modified by the term "about" in all cases. Accordingly, unless indicated to the contrary, the numerical parameters set forth in the specification and accompanying examples are approximations that can vary depending upon the desired properties sought to be obtained. No attempt is made to limit the application of the doctrine of equivalents in any way. For the scope of the embodiments, each numerical parameter should be interpreted in light of at least the number of reported significant digits and by applying 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 the context dictates. Furthermore, generalized steps and operations are provided as examples only, and some of the steps and operations may be optional, combined into fewer steps and operations, or expanded into additional steps and operations.

The invention may sometimes describe different components contained within or connected to different other components. Such depicted architectures are examples only, and many other architectures that achieve the same or similar functionality may be implemented.

Terms used in this disclosure and the accompanying embodiments (eg, the subject matter of the accompanying embodiments) are generally intended to be "open" terms (eg, the term "includes" should be interpreted as "including but not limited to," the term "has" should be interpreted as "at least having", the term "comprising" should be interpreted as "including but not limited to" etc.). In addition, if a specific quantity of an element is introduced, this can be construed to mean at least the recited quantity, as may be indicated by the context (eg, the expression "only two recited items" without other modifiers means two or at least two of the more statements). As used herein, inflectional words and/or phrases presenting two or more alternatives should be understood to be considered to include one of those items, any or all of those items the possibility of such items. For example, the phrase "A or B": should be understood to include the possibility of "A" or "B" or "A and B".

Unless otherwise indicated herein or clearly contradicted by context, the terms "a/an", "the/the" are used in the context of describing the present invention, especially in the context of the following examples. ' and similar demonstratives should be construed to cover both the singular and the plural. The use of any and all examples provided herein, or use of representative language (eg, "such as"), is intended only to better illustrate the invention and is not intended to limit the scope of any embodiment. No language in the specification should be construed as indicating any non-represented element essential to the practice of the invention.

The grouping of alternative elements or embodiments disclosed herein should not be construed as limiting. 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 the group may be available for convenience and/or patentability be included in the group or removed from the group for any reason. When any such inclusion or deletion occurs, this specification is deemed to contain groups modified to satisfy the written description of all Markush groups used in the accompanying embodiments.

Certain embodiments are described herein, including the best mode known to the inventors for carrying out the invention. Of course, variations on these described embodiments will become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventors expect skilled artisans to employ such variations as appropriate, and the inventors intend for the invention to be practiced otherwise than as specifically described herein. Accordingly, the Examples include all modifications and equivalents of the subject matter described in the Examples as permitted by applicable law. Furthermore, any combination of all possible variations of the above elements is contemplated unless otherwise indicated herein or otherwise clearly contradicted by context. Finally, it should be understood that the embodiments disclosed herein are illustrative of the principles of the embodiments. Other modifications that may be employed are within the scope of the embodiments. Thus, by way of example and not limitation, alternative embodiments may be utilized in accordance with the teachings herein. Accordingly, embodiments are not limited to those precisely as shown and described.

Example

其中Z為NR¹⁰、O或S；R⁹選自H、非取代之酯連接基基團、或經取代之酯連接基基團；且R¹⁰選自H、經取代之芳基、非取代之酯連接基基 團、或經取代之酯連接基基團。 Embodiment 1 A photoluminescent composite, the photoluminescent composite comprising: a blue light absorbing azole derivative, the blue light absorbing azole derivative having the following general formula:

wherein Z is ^NR10 , O, or S; ^R9 is selected from H, an unsubstituted ester linker group, or a substituted ester linker group ^; and R10 is selected from H, substituted aryl, unsubstituted an ester linking group, or a substituted ester linking group.

A linker group, wherein the linker group is an unsubstituted ester or a substituted ester; and a boron dipyrrole methylene (BODIPY) moiety; wherein the linker group covalently links the azole derivative to the BODIPY moiety wherein the azole derivative absorbs light energy at a first excitation wavelength and transfers energy to the BODIPY moiety wherein the BODIPY moiety absorbs the energy from the azole derivative and emits light energy at a second higher wavelength , and wherein the emission quantum yield of the photoluminescent complex is greater than 80%.

Embodiment 2 is the azole derivative of Embodiment 1, wherein Z is NR ¹⁰ , R ⁹ is H, and R ¹⁰ is an unsubstituted ester linking group.

Embodiment 3 is the azole derivative of Embodiment 1, wherein Z is NR ¹⁰ , R ⁹ is H, and R ¹⁰ is a substituted ester linking group.

Embodiment 4 is the azole derivative of Embodiment 1, wherein Z is NR ¹⁰ , R ⁹ is an unsubstituted ester linking group, and R ¹⁰ is a substituted aryl group.

Embodiment 5 is the azole derivative of embodiment 1, wherein Z is S, R ⁹ is a substituted ester linking group, and R ¹⁰ is H.

。 Embodiment 6 is the azole derivative of embodiment 4, wherein the substituted aryl group is:

.

其中R¹及R⁶獨立地選自H、飽和或不飽和的烷基基團、或烯基基團；R³及R⁴獨立地選自H或C₁-C₂烷基；R²及R⁵獨立地選自H、飽和烷基、不飽和烷基、氰基(-CN)、烷基酯、或芳基酯；R²及R³可連接在一起以形成另外的單環烴環結構或多環烴環結構；R⁴及R⁵可連接在一起以形成另外的單環烴環結構或多環烴環結構；R⁷及R⁸可獨立地選自H、甲基基團；及L代表連接基基團，該連接基基團包括經取代之酯連接基基團。 Embodiment 7 is the photoluminescent composite of embodiment 1, wherein the BODIPY moiety has the following general formula:

wherein R ¹ and R ⁶ are independently selected from H, saturated or unsaturated alkyl groups, or alkenyl groups; R ³ and R ⁴ are independently selected from H or C ₁ -C ₂ alkyl groups; R ² and ^R5 is independently selected from H, saturated alkyl, unsaturated alkyl, cyano (-CN), alkyl ester, or aryl ester ^; R2 and ^R3 may be joined together to form an additional monocyclic hydrocarbon ring structure or polycyclic hydrocarbon ring structure; R ⁴ and R ⁵ can be linked together to form another monocyclic hydrocarbon ring structure or polycyclic hydrocarbon ring structure; R ⁷ and R ⁸ can be independently selected from H, methyl groups; and L represents a linker group including a substituted ester linker group.

Embodiment 8 is the BODIPY part of embodiment 7, wherein R ¹ , R ³ , R ⁴ and R ⁶ are all methyl groups, R ² and R ⁵ are cyano groups, R ⁷ and R ⁸ are both methyl groups, and L is the linking group.

Embodiment 9 is the BODIPY part of embodiment 7, wherein R ¹ , R ³ , R ⁴ and R ⁶ are all methyl groups, R ² and R ⁵ are selected from substituted esters, and R ⁷ and R ⁸ are both methyl groups, and L is a linking group.

Embodiment 10 is the BODIPY part of embodiment 7, wherein R ¹ , R ³ , R ⁴ and R ⁶ are all methyl groups, R ² and R ⁵ are all aryl esters, R ⁷ and R ⁸ are all methyl groups, and L is a linking group.

Embodiment 11 is the BODIPY moiety of embodiment 7, wherein R ¹ and R ⁶ are each an alkenyl group, R ² and R ³ are joined together to form a monocyclic hydrocarbon ring structure, and R ⁴ and R ⁵ are joined together to form Monocyclic hydrocarbon ring structure, R ⁷ and R ⁸ are each a methyl group, and L is a linking group.

。 Embodiment 12 is the BODIPY moiety of embodiment 7, wherein the alkenyl group has the following structure:

.

R¹及R²連接在一起以形成另外的多環烴環結構；R³及R⁴均為甲基；R⁵及R⁶連接在一起以形成另外的多環烴環結構；R⁷及R⁸可獨立地選自H、甲基或酯基團；且L代表連接基基團，該連接基基團包括經取代之酯連接基基團。 Embodiment 13 is the photoluminescent composite of embodiment 1, wherein the BODIPY moiety has the following general formula:

R ¹ and R ² are linked together to form another polycyclic hydrocarbon ring structure; R ³ and R ⁴ are both methyl; R ⁵ and R ⁶ are linked together to form another polycyclic hydrocarbon ring structure; R ⁷ and R ⁸ can be independently selected from H, methyl or ester groups; and L represents a linker group including a substituted ester linker group.

Embodiment 14 is the BODIPY moiety of embodiment 13, wherein R ¹ and R ² are linked together to form a polycyclic hydrocarbon ring structure, R ³ and R ⁴ are both methyl, and R ⁵ and R ⁶ can be linked together to form a polycyclic hydrocarbon ring structure. Cyclic hydrocarbon ring structure, R ⁷ and R ⁸ are selected from H or methyl (-CH ₃ ), and L is a linking group.

Embodiment 15 is the photoluminescent complex of embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, and 14, wherein the unsubstituted ester linkage is the following:

或

。 Embodiment 16 is the photoluminescent complex of embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and 11, wherein the substituted ester of the linking group is selected from the following structures One of the structures:

or

.

Embodiment 17 is the photoluminescent composite of embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, and 14, wherein the photoluminescent composite is selected from the group consisting of One of the structures:

Embodiment 18 A color conversion film, the color conversion film comprising: a transparent substrate layer; a color conversion layer, wherein the color conversion layer comprises a resin matrix, and at least one photoluminescent compound, wherein the at least one photoluminescent compound comprises as The photoluminescent compounds of Examples 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 and 13 dispersed in the resin matrix.

Example 19 is the color conversion film of Example 18, which also includes a singlet oxygen quencher.

Example 20 is the color conversion film of Example 18, which also includes a free radical scavenger.

Embodiment 21 is the color conversion film of Embodiment 18, wherein the thickness of the film is between 10 μm and 200 μm.

Embodiment 22 is the color converting film of embodiment 18, 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 510 nm to about 560 nm and 575 nm to about 645 nm.

Embodiment 23 A method of preparing the color conversion film of Embodiment 18, 19, 20 and 21, the method comprising: mixing the color conversion films of Embodiment 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, The photoluminescent composites and binder resins of 11, 12, 13, 14, 15, 16, and 17 are dissolved in a solvent; and the mixture is applied to one of the opposing surfaces of the transparent substrate.

Embodiment 24 is a backlight unit comprising the color conversion films of Embodiments 18, 19, 20 and 21.

Embodiment 25 is a display device including the backlight unit of Embodiment 24.

example

Embodiments of the photoluminescent composites described herein have been found to have improved performance compared to other forms of dyes used in color conversion films. It is further demonstrated by the following examples With these benefits, the examples are intended only to illustrate the invention and are not intended to limit the scope or rationale in any way.

Example 1.1 Comparative Example 1 (CE-1):

CE-1: 0.75 g of 4-hydroxy-2,6-dimethylbenzaldehyde (5 mmol) and 1.04 g of 2,4-dimethylpyrrole (11 mmol) were dissolved in 100 mL of anhydrous dichloromethane. The solution was degassed for 30 minutes. One drop of trifluoroacetic acid was then added. The solution was stirred at room temperature overnight under an argon atmosphere. To the resulting solution was added DDQ (2.0 g), and the mixture was stirred overnight. The solution was filtered the next day and washed with dichloromethane to give dipyrrolemethane (1.9 g). Next, 1.0 g of dipyrrolemethane was dissolved in 60 mL of THF. 5 mL of trimethylamine was added to the solution and then degassed for 10 minutes. After degassing, 5 mL of boron trifluoro-diethyl ether was added slowly, followed by heating at 70°C for 30 minutes. The resulting solution was loaded onto silica gel and purified by flash chromatography using dichloromethane as eluent. The desired fractions were collected and dried under reduced pressure to give 0.9 g of an orange solid (76% yield). LCMS (APCI+): _calcd for _C21H24BF2N2O ( _{M +} H) = 369; found: 369. ¹ H NMR (400 MHz, chloroform- d ) δ 6.64(s, 2H), 5.97(s, 2H), 4.73(s, 1H), 2.56(s, 6H), 2.09(s, 6H), 1.43(s, 6H).

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

Example 2: Synthesis of Photoluminescent Complex:

Example 2.1: PLC-1

Compound 1.1 (4-(4-((4-(7-(4-(diphenylamino)phenyl)benzo[c][1,2,5]thiadiazol-4-yl)phenyl )(phenyl)amino)phenyl)-4-side oxybutyric acid) :

Step 1: Compound 1.1.1(4-(4-((4-(7-(4-(diphenylamino)phenyl)benzo[c][1,2,5]thiadiazole-4 -yl)phenyl)(phenyl)amino)phenyl)-4-pentoxybutyric acid methyl ester): A 300 mL 3-neck round bottom flask was charged with a stir bar and purged with argon. To the flask was added 4,4'-(benzo[c][1,2,5]thiadiazole-4,7-diyl)bis(N,N-diphenylaniline at room temperature with stirring ) (prepared according to US 9,399,730B2, 1.00 mmol, 623 mg), dry DCM ( ₂₀ mL), followed by ZnCl2 (1.0 M in _Et2O , 6.0 mmol, 6.00 mL). To the stirred mixture was added methyl 4-chloro-4-pentoxybutyrate (5.0 mmol, 0.616 mL) via syringe. The reaction mixture was stirred at room temperature for 24 hours, then heated to 50°C under argon for 2 days. The reaction mixture was cooled to room temperature and partitioned with DCM (250 mL) and water (100 mL). The layers were separated, the aqueous layer was extracted with DCM (2 x 20 mL), the combined organic layers were washed with brine (20 mL), dried over _MgSO4 , filtered and concentrated in vacuo. Purified by flash chromatography on silica gel using ethyl acetate/DCM gradient (100% DCM (1 CV)→10% EtOAc/DCM (10 CV)). 248 mg of compound 1.1.1 were obtained (34% yield). MS (APCI): Calculated for _{C47H36N4O3S (} MH) ₌ 735; found= ₇₇₃₅ . ¹ H NMR (400MHz, chloroform- d )δ 7.95(d, J =8.2Hz, 2H), 7.88(t, J =7.8Hz, 4H), 7.77(s, 2H), 7.37(t, J =7.7Hz ,2H),7.33-7.22(m,6H),7.24-7.15(m,8H),7.12(d, J =8.5Hz,2H),7.07(t, J =7.4Hz,2H),3.71(s, 3H), 3.27(t, J =6.7Hz, 2H), 2.76(t, J =6.7Hz, 2H).

Step 2: Compound 1.1(4-(4-((4-(7-(4-(diphenylamino)phenyl)benzo[c][1,2,5]thiadiazol-4-yl )phenyl)(phenyl)amino)phenyl)-4-pendoxobutanoic acid) : A 250 mL 3-neck round bottom flask was charged with a stir bar and flushed with argon. To compound 1.1.1 was added KOH (3.26 mmol, 183 mg) followed by water (5 mL). The flask was fitted with a finned air condenser and heated to 95°C in an aluminum heating block with vigorous stirring under argon. The reaction mixture was heated until LCMS showed no starting material (2 hours). A 1 L Erlenmeyer flask was charged with a stir bar and crushed ice (500 mL unpackaged). The warm reaction mixture was added to the flask with stirring. The product was precipitated by adding 6N aqueous HCl to pH 3.5-4 (pH paper). The mixture was diluted with water to a total volume of 750 mL and stirred for several hours, warming to room temperature. The product was isolated by filtration and dried in vacuo to give quantitative yield. MS (APCI): Calculated for _{C46H34N4O3S (} MH _{) =} 721; found=721. The product was of sufficient purity to be used in the next step.

Compound 1.2: (3,3'-(7,7-Difluoro-14-(4'-hydroxy-[1,1'-biphenyl]-4-yl)-1,3,4,7,10 ,11,12,13-Octahydro-2H-6l4,7l4-[1,3,2]diazaborabenzo[4,3-a:6,1-a']diisoindole-5 ,9-diyl)(2E,2'E)-diethyl diacrylate) :

Compound 1.2.1 (3,3'-((4-bromophenyl)methylene)bis(4,5,6,7-tetrahydro-2H-isoindole-1-carboxylic acid diethyl ester)) : A 500 mL round bottom flask was charged with a stir bar and flushed with argon. To the flask were added ethyl 4,5,6,7-tetrahydro- 2H -isoindole-1-carboxylate (10.0 mmol, 1.933 g) and 4-bromobenzaldehyde (6.00 mmol, 1110 mg). Anhydrous dichloromethane (200 mL) was added followed by p-TsOH (0.1 g). The flask was sealed and stirred at room temperature under argon overnight. The reaction mixture was evaporated to dryness and the residue was saponified without further purification. MS (APCI): _calcd for _{C29H33BrN2O4 (} MH ₎ = 551; found: 551.

Compound 1.2.2 (14-(4-Bromophenyl)-7,7-difluoro-5,9-diiodo- 1,3,4,7,10,11,12,13-octahydro-2H- 614,714-[1,3,2]diazaborabenzo[4,3-a:6,1-a']diisoindole): A 1 L round bottom flask was charged with a stir bar. To the flask was added NaOH (6.00 g) and water (30 mL). The mixture was stirred to obtain a solution, and the flask was flushed with argon. Compound 1.2.1 (assume 5.0 mmol) was added to the reaction flask followed by ethanol (200 proof, 300 mL). The flask was fitted with a finned air condenser and heated in an oil bath at 90°C under an argon atmosphere. After heating overnight, the reaction mixture was cooled to room temperature and transferred to a 1 L Erlenmeyer flask. While stirring in an ice-water bath, the pH was adjusted to 4 with 6N aqueous HCl. The mixture was diluted with water to a total volume of 1 L and the precipitate was collected via suction filtration. The moist precipitate was placed in a 3 L 2 neck round bottom flask and the flask was charged with a stir bar. The flask was flushed with argon. A solution of sodium bicarbonate (188.2 mmol, 15.81 g) was prepared in water (300 mL) and added to the reaction flask. Methanol (900 mL) was added with stirring to obtain a solution. Under argon atmosphere, iodine (58.8 mmol, 14.92 g) was added to the flask with vigorous stirring. The reaction mixture was stirred at room temperature overnight. The precipitated intermediate was filtered off and washed with water. The product was dried by suction and then dried in a vacuum oven at 50°C. The dried precipitate was dissolved in dry dichloromethane (500 mL) in an argon flushed 1 L 2 neck round bottom flask equipped with a stir bar. The flask was sealed with a septum and cooled to -10°C under an argon atmosphere (water-ice/methanol bath). To the flask was added _BF3 by syringe with vigorous stirring. _OEt2 (571.2 mmol, 70.5 mL). The flask was fitted with a dropping funnel, and anhydrous triethylamine (331.5 mmol, 46.2 mL) was placed in the dropping funnel. Triethylamine was added dropwise over 5 minutes with vigorous stirring. The cooling bath was removed and the reaction mixture was stirred under an argon atmosphere and warmed to room temperature. The reaction was stirred overnight. The reaction was quenched by the addition of IN aqueous HCl (200 mL). The layers were separated and the organic layer was washed sequentially with IN aqueous HCl (200 mL), saturated aqueous sodium bicarbonate (3 x 200 mL), and brine (200 mL). The organic layer was dried over _MgSO4 , filtered, and concentrated by rotary evaporation. To the crude purple-black liquid was added methanol. The mixture was concentrated to dryness on celite and then purified by flash chromatography using a hexane/toluene gradient (80% toluene/hexane→100% toluene) to give 1.888 g of the desired product (yield 64%). MS (APCI) _: Calculated for _{C23H20BBrF2I2N2 ( MH )} = 705; found: 705.

Compound 1.2.3 (3,3'-(14-(4-bromophenyl)-7,7-difluoro-1,3,4,7,10,11,12,13-octahydro-2H-6l4 ,7l4-[1,3,2]diazaborabenzo[4,3-a:6,1-a']diisoindole-5,9-diyl)(2E,2'E) - Diethyl diacrylate): A 250 mL 2-neck round bottom flask was charged with a stir bar and equipped with a reflux condenser and flushed with argon. To the flask were added compound 1.2.2 (0.500 mmol, 353 mg), Pd(dppf)Cl ₂ (0.067 mmol, 49 mg) and phenylboronic acid (5.05 mmol, 616 mg). Inhibitor-free THF (20 mL) and toluene (20 mL) were added, followed by 1.0 M K ₂ CO ₃ aqueous solution (5.05 mmol, 5.05 mL). The flask was purged with oxygen three times by vacuum/backfill argon cycle. The flask was heated in an oil bath at 70°C for four hours. Another portion of phenylboronic acid (5.05 mmol, 616 _mg ) and aqueous K2CO3 (5.05 mL) _were added, and the reaction was heated at 70 °C for an additional 2 h. The reaction mixture was cooled to room temperature and partitioned with ethyl acetate (150 mL). The mixture was washed with saturated aqueous sodium bicarbonate (3 x 25 mL) and brine (25 mL). The reaction mixture was dried over _MgSO4 , filtered, and concentrated to dryness on a rotary evaporator. The crude product was purified by flash chromatography using an ethyl acetate/hexane gradient (30% ethyl acetate/hexane (1 CV)→100% ethyl acetate/hexane (10 CV)). The fractions containing the product were concentrated in vacuo and triturated with methanol to remove co-eluting impurities. 178 mg of compound 1.2.3 were obtained (55% yield). MS (APCI): _calcd for _{C33H34BBrF2N2O4 (} MH ₎ = 649 _; found: 649.

Compound 1.2 (3,3'-(7,7-Difluoro-14-(4'-hydroxy-[1,1'-biphenyl]-4-yl)-1,3,4,7,10, 11,12,13-Octahydro-2H-6l4,7l4-[1,3,2]diazaborabenzo[4,3-a:6,1-a']diisoindole-5, 9-Diyl)(2E,2'E)-diethyl diacrylate) : A 250 mL 2-neck round bottom flask was charged with a stir bar and equipped with a reflux condenser and flushed with argon. To the flask were added compound 1.2.3 (0.263 mmol, 171 mg), Pd(dppf)Cl ₂ (0.067 mmol, 49 mg) and a phenylboronic acid derivative (5.05 mmol, 616 mg). Inhibitor-free THF (20 mL) and toluene (20 mL) were added, followed by 1.0 M K ₂ CO ₃ aqueous solution (5.05 mmol, 5.05 mL). The flask was purged with oxygen three times by vacuum/backfill argon cycle. The flask was heated in an oil bath at 80°C for four hours. Another portion of the phenylboronic acid derivative (5.05 mmol, 616 _mg ) and aqueous K2CO3 (5.05 mL) _were added, and the reaction was heated at 70 °C for an additional 2 h. The reaction mixture was cooled to room temperature and partitioned with ethyl acetate (150 mL). The mixture was washed with saturated aqueous sodium bicarbonate (3 x 25 mL) and brine (25 mL). The reaction mixture was dried over _MgSO4 , filtered, and concentrated to dryness on a rotary evaporator. The crude product was purified by flash chromatography using an ethyl acetate/hexane gradient (30% ethyl acetate/hexane (1 CV)→100% ethyl acetate/hexane (10 CV)). The fractions containing the product were concentrated in vacuo and triturated with methanol to remove co-eluting impurities. 158 mg of compound 1.2 were obtained (90% yield). MS (APCI): _calcd for _{C39H39BF2N2O5 (} MH ₎ = 663 _; found: 663. (MH) Calculated = 983; Found: 983.

PLC-1(3,3'-(14-(4'-((4-(4-((4-(7-(4-(diphenylamino)phenyl)benzo[c][1 ,2,5]thiadiazol-4-yl)phenyl)(phenyl)amino)phenyl)-4-oxybutanoyl)oxy)-3,5-dimethyl-[1,1' -Biphenyl]-4-yl)-7,7-difluoro-1,3,4,7,10,11,12,13-octahydro-2H-6l4,7l4-[1,3,2] Diazaborabenzo[4,3-a:6,1-a']diisoindole-5,9-diyl)(2E,2'E)-diethyl diacrylate): in 40 mL A screw cap vial was charged with compound 1.2 (0.060 mmol, 42 mg) and compound 1.1 (0.120 mmol, 87 mg), DMAP (0.182 mmol, 22 mg) and a stir bar. The vial was sealed with a screw cap septum and flushed with argon. To the vial was added dry THF (6 mL) followed by DIC (0.182 mmol, 38 mg). After stirring overnight under argon at room temperature, water (35 mL) was added and the resulting precipitate was filtered off and washed with water. The wet precipitate was dissolved in DCM, separated from water, dried over _MgSO4 , filtered, and concentrated in vacuo. The product was purified by flash chromatography using an ethyl acetate/DCM gradient (100% DCM (1 CV)→10% ethyl acetate/DCM (10 CV)). The product containing fractions were concentrated in vacuo to give 54 mg of PLC-1 (65% yield). MS (APCI): _calcd for _{C73H75BF2N2O6 (} MH ₎ = 1395 _; found: 1395.

Example 2.2: PLC-2:

Compound 2.1.1 Methyl 5-(4,7-bis(4-(diphenylamino)phenyl)-2H-benzo[d][1,2,3]triazol-2-yl)pentanoate ester

Step 1: 4,7-Dibromo-2H-benzo[d][1,2,3]triazole: To 42 mL of stirring deionized aqueous solution was added 2.85 g (41.4 mmol, 1.1 equiv) of sodium nitrite. The solution was then slowly added to 42 mL of cooled glacial acetic acid. After mixing for about 10 minutes, 10 g (37.6 mmol, 1 equiv.) of 3,6-dibromobenzene-1,2-diamine was added. After the addition was complete, the cooling bath was removed. After stirring at room temperature for about 2 hours, the solution was filtered. The collected precipitate was then dried in a room temperature vacuum oven overnight. The desired product was obtained as a beige powder (9.3 g, 89% yield). ¹ H NMR (400 MHz, DMSO-d6): δ 6.64 (s, 1H), 5.01 (s, 2H).

Step 2: Methyl 5-(4,7-dibromo-2H-benzo[d][1,2,3]triazol-2-yl)pentanoate: In a small flask, mix 2 g (7.2 mmol, 1 equiv) 4,7-dibromo-2H-benzo[d][1,2,3]triazole, 15.5 mL (21 mmol, 15 equiv) methyl 5-bromovalerate. 20 mL of N,N'-dimethylformamide was added. Then 5 g (36 mmol, 5 equiv) of potassium carbonate were added. The solution was heated at 75°C for about 1.5 hours. The reaction was placed on 500 g ice water and extracted with 300 mL dichloromethane. The reaction was dried on silica gel and purified via silica gel chromatography using hexane:ethyl acetate (9:1) as eluent. The desired product was obtained as a clear viscous liquid (1.8 g, 64% yield). ¹ H NMR (400MHz, TCE-d2): δ 7.38(s, 2H), 4.72(t, 2H), 3.58(s, 3H), 2.31(t, 2H), 2.11(p, 2H), 1.59(m , 3H).

Step 3: Methyl 5-(4,7-bis(4-(diphenylamino)phenyl)-2H-benzo[d][1,2,3]triazol-2-yl)pentanoate : Mix 1.8 g (4.6 mmol, 1 equiv) methyl 5-(4,7-dibromo-2H-benzo[d][1,2,3]triazol-2-yl)pentanoate in a small flask , 10 mL of n-butanol, 3 mL of toluene and 3 mL of deionized water. The solution was bubbled with argon for about 30 minutes. Subsequently, 3.99 g (13.81 mmol, 3 equiv) of (4-(diphenylamino)phenyl)boronic acid was added, followed by 6 g (56.61 mmol, 12.30 equiv) of potassium carbonate. Then 1.06 g (0.920 mmol, 0.2 equiv) of tetrakis(triphenylphosphine)palladium(0) was added. The solution was heated at 110°C for about 3 hours. The reaction was dried on silica gel and purified via silica gel chromatography using hexane:ethyl acetate (9:1) as eluent. The desired product, compound 2.1.1 (300 mg, 10% yield) was obtained as a yellow powder. ¹ H NMR (400MHz, TCE-d2): δ 7.95(d, 4H), 7.55(s, 2H), 7.23(t, 8H), 7.12(m, 12H), 7.00(t, 4H), 4.73(t , 2H), 3.53 (s, 3H), 2.32 (t, 2H), 2.13 (p, 2H), 1.66 (p, 2H).

Compound 2.1 (5-(4,7-bis(4-(diphenylamino)phenyl)-2H-benzo[d][1,2,3]triazol-2-yl)pentanoic acid): A 100 mL 2-neck round bottom flask was charged with 5-(4,7-bis(4-(diphenylamino)phenyl)-2H-benzo[d][1,2,3]triazole- 2-yl)pentanoate methyl ester (compound 2.1.1, 0.425 mmol, 306 mg), and the flask was suspended in absolute ethanol (80 mL). The flask was fitted with a finned reflux condenser and flushed with argon. The reaction mixture was treated with potassium hydroxide (12.7 mmol, 713 mg) and heated to 90°C and stirred at this temperature for 6 hours under argon. The reaction was cooled to room temperature, and the reaction mixture was evaporated to dryness. The crude product was dispersed in water (250 mL) and acidified to pH about 1 with 6N HCl. After acidification, the crude acid was isolated by precipitation from water to give 289 mg of compound 2.1 (96% yield). This acid was used in the next step without further purification. MS (APCI): Calculated for formula C ₄₇ H ₃₉ N ₅ O ₂ (M-)=705; found: 705.

Compound 2.2:

Compound 2.2.1 (4,5-dihydro-1H-benzo[g]indole): DMSO (50 mL), KOH (3.36 g) and NH ₂ OH. The mixture of HCl (4.17g) was stirred at room temperature for 30 minutes, then a solution of 1-tetralone (7.3g) in DMSO (25ml) was added. The mixture was stirred at 70°C for another 30 minutes. KOH (8.41 g) was then added and the resulting mixture was heated to 140°C and a solution of 1,2-dichloroethane (9.9 g) in DMSO (25 mL) was added dropwise over 4 hours. After cooling to room temperature, the solution was poured into 200 mL of saturated _NH4Cl solution, and the solution was extracted with ethyl acetate (200 mL x 3). The organic phases were collected and dried _{over Na2SO4} , concentrated to 10 mL, then diluted with 10 mL of dichloromethane and 50 mL of hexanes. The solution was flash chromatographed (silica gel) using dichloromethane/hexane (0%→30%) eluent and the second main fraction was collected. After removing the solvent under reduced pressure, a pale yellow solid compound 2.2.1 was obtained (3.5 g, 41% yield). LCMS (APCI+): _calcd for _C12H12N (M+H): 170; found: 170.

Compound 2.2.2 (4-(bis(4,5-dihydro-1H-benzo[g]indol-2-yl)methyl) -3,5-dimethylphenol): compound 2.2.1 (0.34 g, 2 mmol), a mixture of 4-hydroxy-2,5-dimethylbenzaldehyde (0.15 g, 1 mmol) and a drop of trifluoroacetic acid in 1,2-dichloroethane (20 mL) were degassed for 10 min , and then stirred at 30 °C for 20 h. After cooling to room temperature, the mixture was filtered, and the solid was collected as compound 2.2.2 (0.2 g, 43% yield). LCMS (APCI+): _calcd for _C33H31N2O (M+H): ₄₇₁ ; found: 471.

Compound 2.2: To a solution of compound 2.2.2 (200 mg, 0.42 mmol) in 20 mL of dichloromethane was added tetrachlorobenzoquinone (100 mg, 0.45 mmol) at 0°C using ice-water bath cooling. The mixture was stirred for 20 minutes. To the resulting mixture was then added 0.5 mL of trimethylamine followed by 0.8 mL of _BF3 -etherate. The bulk was stirred at room temperature overnight, then loaded onto silica gel and purified by flash chromatography using dichloromethane/hexane (0%→80%) eluent. Collect the desired red luminescent fraction. After removal of the solvent, a metallic dark red solid compound 2.2.2 was obtained (150 mg, 72% yield). LCMS (APCI ₊ ): _calcd for _C33H28BF2N2O (M ₊ H): 517; found: 517.

PLC-2: ((T-4)-[2-[(4,5-dihydro-2H-benzo[g]indole-2-ylidene-k N )-(3,5-dimethyl -4-(5-(4,7-bis(4-(diphenylamino)phenyl)-2H-benzo[d][1,2,3]triazol-2-yl)valerate )phenyl)methyl]-4,5-dihydro-1H-benzo[g]indole - kN]difluoroboron): a 40 mL screw cap vial was charged with a stir bar, compound 2.1 (0.050 mmol, 32 mg) and compound 2.2 (0.060 mmol, 42 mg), and DMAP:pTsOH 1:1 salt (0.200 mmol, 59 mg). The vial was flushed with argon and dry dichloromethane (20 mL) was added. Diisopropylcarbodiimide (0.300 mmol, 47 uL) was added and the reaction was stirred overnight at room temperature under argon. The next morning, dry tetrahydrofuran (10 mL) was added and sonicated for 30 seconds. Another portion of compound 2.1 was added and stirred overnight at 50°C under argon. by flash chromatography on silica gel (100% hexane (1 CV)→50% DCM/hexane (0 CV)→100% DCM (6 CV)→10% EtOAc/DCM (10 CV)) The crude product was purified. The product containing fractions were collected and evaporated to dryness to give 43 mg of PLC-2 (65% yield). MS (APCI): Calculated for formula C ₈₀ H ₆₄ BF ₂ N ₇ O ₂ (M-) = 1203; found: 1203. ¹ H NMR (400MHz, chloroform-d)δ 8.80(d,J=8.0Hz,2H),8.01(d,J=8.8Hz,4H),7.61(s,2H),7.45(t,J=7.7Hz ,2H),7.35-7.27(m,10H),7.25-7.15(m,14H),7.07-7.01(m,4H),6.84(s,2H),6.29(s,2H),4.88(t,J =7.0Hz,2H),2.90(t,J=7.2Hz,4H),2.68(t,J=7.3Hz,2H),2.63(t,J=7.0Hz,4H),2.34(p,J=7.9 , 7.3Hz, 2H), 2.18(s, 3H), 1.90(p, J=7.7, 7.1Hz, 2H).

Example 2.3: PLC-3

Compound 3.1 (4-(6',6'-difluoro-6'H-5'l4,6'l4-bispiro[cyclopentane-1,12'-indeno[2',1':4 ,5]pyrrolo[1,2-c]indeno[2',1':4,5]pyrrolo[2,1-f][1,3,2]diazaborin-16',1"-Cyclopentane]-14'-yl)-3,5-dimethylphenol: Step 1: (1-(2-Bromophenyl)cyclopent-1-ol): 250mL in oven A 2-neck round-bottomed flask was fitted with a gas adapter and a stirring bar, and was flushed with argon. The flask was sealed with a septum and filled with magnesium turnings (145 mmol, 3.525 g) and anhydrous THF (100 mL) via a syringe. Dry 100 mL of 2 The necked round bottom flask was fitted with a gas adapter and flushed with argon. The flask was sealed with a septum and charged with dry THF (60 mL). To the 100 mL flask was added 1,5-dibromopentane (70.0 mmol, 8.30 mL). The 250 mL flask was cooled in an ice water bath at 0°C and the 1,5-dibromopentane solution was added via syringe over 5 minutes with vigorous stirring. The ice water bath was removed and replaced with a room temperature water bath, And the reaction mixture was stirred at room temperature. The reaction became slightly cloudy when stirred at room temperature for 4 hours. A 1000 mL 2-neck round bottom flask was fitted with a gas adapter and stir bar and flushed with argon. The second The neck was sealed with a septum, and dry THF (60 mL) was added. To the flask was added ethyl 2-bromobenzoate (50.0 mmol, 7.94 mL) with stirring at room temperature. The flask was cooled to 0°C in an ice-water bath , and the double Grignard solution was added via cannula with vigorous stirring in about 5 minutes. The reaction mixture was stirred at 0° C. for 15 minutes and then at room temperature for 3 hours. The reaction mixture was cooled to 0° C. and used Quenched with saturated ammonium chloride solution (50 mL). The reaction mixture was further diluted with water (500 mL) and extracted with ethyl acetate (3 x 150 mL). The combined organic layers were washed with brine (150 mL), dried over _MgSO4 , Filtered and evaporated to dryness to give a pale yellow oil. This oil was pure enough to be used in the next step. Obtained _11.145 g (92% yield). MS (APCI): _C11H13BrO Calculated value of (M+H)=241; found value: 241.

Step 2: (3-(1-(2-Bromophenyl)cyclopentyl)-1-toluenesulfonyl-1H-pyrrole/2-(1-(2-bromophenyl)cyclopentyl)-1 -Tosyl-lH-pyrrole): A 250 mL 2-neck round bottom flask was charged with a stir bar and fitted with a gas adapter. The flask was flushed with argon, and 1-(2-bromophenyl)cyclopent-1-ol (10.0 mmol, 2.412 g) was added to the flask. Anhydrous dichloromethane (100 mL) was added, and 1-toluenesulfonyl-1H-pyrrole (11.0 mmol, 2.434 g) was added with stirring at room temperature. To the stirred mixture was added aluminum chloride (11.5 mmol, 1.533 g) in one portion. The reaction was stirred overnight at room temperature under argon. The reaction was quenched with water (30 mL) with vigorous stirring. The layers were separated and the aqueous layer was extracted with dichloromethane (3 x 25 mL). The combined organic layers were washed with brine (25 mL), dried over _MgSO4 , filtered, and evaporated to dryness. The crude product was purified by flash chromatography on silica gel (100% hexanes (1 CV)→15% EtOAc/hexanes (10 CV)). The two possible isomers elute as a singlet on silica gel and also co-elute with unreacted 1-toluenesulfonyl-1H-pyrrole as 1.311 g. About 1.05 g of product was estimated by ¹ H NMR in 23% yield. The mixture was submitted to the next step without further purification. MS (APCI): _calcd for _C22H22BrNO2S (M ₊ H) = 444; found: 444.

Step 3: (2-(1-(2-Bromophenyl)cyclopentyl)-1-toluenesulfonyl-1H-pyrrole) A 40 mL screw cap vial was charged with a stir bar. To the vial was added the mixture from Step 2 (estimated 2.37 mmol, 1.05 g). The vial was flushed with argon. To the vial was added potassium carbonate (4.86 mmol, 672 mg), Pd( _PPh3 ) ₄ (0.0711 mmol, 82 mg) and anhydrous dimethylformamide (6 mL). The vial was purged of oxygen by vacuum/backfill argon cycles (3 times). The reaction mixture was stirred in a heating block at 110 °C overnight under argon. The next morning, more potassium carbonate (4.86 mmol, 672 mg) and Pd( _PPh3 ) ₄ (0.0711 mmol, 82 mg) were added and heating was continued at 110°C for an additional 24 hours. The reaction mixture was cooled to room temperature, diluted with water (100 mL), and extracted with ether (3 x 50 mL). The combined organic layers were washed with water (3 x 25 mL), brine (25 mL), dried over _MgSO4 , filtered, and evaporated to dryness. The crude reaction mixture was purified by flash chromatography on silica gel (10% DCM/hexane (1 CV)→50% DCM/hexane (10 CV)). The desired product was co-eluted with ¹ -toluenesulfonyl-1H-pyrrole and the yield estimated by1H NMR was 549 mg, 64% yield. The mixture of the desired isomer and 1-toluenesulfonyl-1H-pyrrole was sent to the next step without further purification. MS (APCI): Calculated for _C22H21NO2S (M ₊ H) = ₃₆₄ ; found: 364.

Step 4: (1'H-spiro[cyclopentane-1,4'-indeno[1,2-b]pyrrole]): A 100 mL 2-neck round bottom flask was charged with a stir bar and fins were assembled Chip condenser and gas adapter. The flask was flushed with argon and the mixture from step 3 (estimated 1.8 mmol, 819 mg mixture) was added followed by tetrahydrofuran (BHT inhibited, 50 mL) and methanol (15 mL). To the flask was added KOH (18.0 mmol, 1.01 g). The second neck was stoppered and the flask was placed in the heating block. The reaction mixture was stirred at 65°C for 12 hours under argon. The solvent was evaporated to dryness and the residue was dispersed in saturated ammonium chloride (25 mL) and water (100 mL). The product was filtered off, washed with water, dried, and purified by flash chromatography on silica gel (100% hexanes (1 CV)→20% EtOAc/hexanes (10 CV)). Fractions containing product were evaporated to dryness to give 279 mg (74% yield) without any contaminants. MS ( _APCI ): Calculated for _C15H15N (M+H) = 210; found: 210. ¹ H NMR (400MHz, chloroform-d) δ 8.24(s, 1H), 7.33(dt, J=7.5, 1.0Hz, 1H), 7.24-7.17(m, 2H), 7.08(td, J=7.2, 1.7 Hz, 1H), 6.81 (t, J=2.5Hz, 1H), 6.19 (dd, J=2.7, 1.8Hz, 1H), 2.16-2.02 (m, 6H), 1.89-1.74 (m, 2H).

Compound 3.1 (4-(6',6'-difluoro-6'H-5'l4,6'l4-bispiro[cyclopentane-1,12'-indeno[2',1':4 ,5]pyrrolo[1,2-c]indeno[2',1':4,5]pyrrolo[2,1-f][1,3,2]diazaborin-16',1"-Cyclopentane]-14'-yl)-3,5-dimethylphenol): In a 250 mL 2-neck round bottom flask equipped with a finned condenser, stir bar and gas adapter. Use argon The flask was rinsed and 1'H-spiro[cyclopentane-1,4'-indeno[1,2-b]pyrrole] (product from step 4 above) (1.31 mmol, 275 mg) and 4-hydroxy were added -2,6-Dimethylbenzaldehyde (0.683 mmol, 103 mg) followed by addition of anhydrous dichloroethane (50 mL). The solution was stirred and bubbled with argon for 30 minutes, then trifluoroacetic acid (0.1%) was added via syringe v/v, 50 uL) and continued argon bubbling for an additional 10 minutes. The spray needle was removed, and the reaction mixture was stirred at room temperature under argon overnight. The next morning, the reaction mixture was cooled with an ice-water bath to 0 °C and p-tetrachlorobenzoquinone (0.655 mmol, 161 mg) was added with stirring. The reaction was stirred at 0 °C for 20 minutes at which time the oxidation was complete. To the reaction was added _{BF3.OEt2 (} 14.67 mmol, 1.8 mL) and triethylamine (8.78 mmol, 1.2 mL), and the mixture was stirred at 0°C and slowly warmed to room temperature over 4 hours. The water bath was removed and replaced with a heating block, and the reaction was heated at 40°C Heated for 6 hours. The reaction mixture was evaporated to dryness and treated with methanol (10 mL) and water (200 mL). The precipitate was stirred at room temperature for 30 minutes, then filtered off and washed with water. Purified by flash chromatography on silica gel (100% DCM (4 CV)→5% EtOAc/DCM (5 CV)→5% EtOAc/DCM). The column was eluted until the tail product had eluted. Fractions were evaporated to dryness to give 314 mg (85% yield). MS (APCI) ^: _calcd for _{C39H35BF2N2O (} M- ₎ = 596; found 596.

PLC-3: (4-(4-((4-(7-(4-(diphenylamino)phenyl)benzo[c][1,2,5]thiadiazol-4-yl) Phenyl)(phenyl)amino)phenyl)-4-oxobutanoic acid 4-(6',6'-difluoro-6'H-5'l4,6'l4-bispiro[ring Pentane-1,12'-indeno[2',1':4,5]pyrrolo[1,2-c]indeno[2',1':4,5]pyrrolo[2,1- f][1,3,2]diazaborin-16',1"-cyclopentane]-14'-yl)-3,5-dimethylphenyl ester): from compound 3.1 (0.100 mmol , 60 mg) and compound 1.1 (0.400 mmol, 289 mg) were synthesized in a manner similar to compound 2. PLC-3 was synthesized by flash chromatography on silica gel (30% DCM/hexane (1 CV)→50% DCM/ The crude product was purified with hexane (8 CV)→100% DCM (8 CV). The fractions containing the product were evaporated to dryness to give 84 mg of PLC-3 (65% yield). MS (APCI): formula Calculated for _{C85H67BF2N6O3S (} M- _{) =} 1300 _; found: 1300.

Example 2.4: PLC-4

PLC-4 ((T-4)-[2-[(4,5-Dihydro-2H-benzo[g]indole-2-ylidene-kN)-(3,5-dimethyl-4 -(4-(4-((4-(7-(4-(diphenylamino)phenyl)benzo[c][1,2,5]thiadiazol-4-yl)phenyl) (Phenyl)amino)phenyl)-4-oxobutyrate)phenyl)methyl]-4,5-dihydro-1H-benzo[g]indole-kN]difluoroboron) : A 40 mL screw cap vial was charged with a stir bar, compound 2.2 (0.100 mmol, 60 mg), compound 1.1 (0.150 mmol, 51 mg), and DMAP:pTsOH 1:1 salt (0.200 mmol, 59 mg). The vial was flushed with argon and dry dichloromethane (20 mL) was added. Diisopropylcarbodiimide (0.300 mmol, 47 uL) was added and the reaction was stirred overnight at room temperature under argon. The next morning, dry tetrahydrofuran (10 mL) was added and sonicated for 30 seconds. Another portion of compound 1.1 (0.150 mmol, 51 mg) was added and stirred at 50 °C overnight under argon. by flash chromatography on silica gel (100% DCM (5 CV)→5% EtOAc/DCM (5 CV), then 10% EtOAc/hexanes (1 CV)→20% EtOAc/hexanes (0 CV) )→50% EtOAc/hexane (10 CV) and finally 5% EtOAc/toluene (1 CV)→15% EtOAc/toluene (10 CV)) to purify the crude product. Fractions containing product were evaporated to dryness to give 40 mg of PLC-4 (33% yield). MS (APCI): Calculated for _{formula C79H59BF2N6O3S (} M-) ₌ 1220 _; found: 1220.

Example 2.5: PLC-5

Compound 5.1 [5,5-Difluoro-10-(4-hydroxy-2,6-dimethylphenyl)-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[ 1,2-c: 2',1'-f][1,3,2]diazaborin-2,8-dicarboxylate dibenzyl ester] :

In a 250 mL round bottom flask, 40 mL (241 mmol) of tert-butyl 3-pentoxybutyrate was dissolved in 80 mL of acetic acid. The mixture was cooled to about 10°C in an ice-water bath. Sodium nitrite (18 g, 262 mmol) was added over 1 hour while keeping the temperature below 15°C. The cold bath was removed and the mixture was stirred at room temperature for 3.5 hours. The insolubles were filtered off to give a crude solution of the oxime, which was used in the next step without further purification. Next, 50 g of zinc powder (0.76 mol) was added portionwise to a mixture of 13.7 mL (79 mmol) of benzyl 3-pendoxobutyrate and 100 mL of acetic acid. The resulting mixture was stirred in an oil bath and heated to 60°C. The crude solution of 3-butyl 2-(hydroxylamino)-3-pendoxobutyrate was added slowly. The temperature was then raised to 75°C and stirred for 1 hour. Next, the reaction mixture was poured into water (4 L). The precipitate was collected and filtered to give benzyl 2,4-dimethyl- lH -pyrrole-3-carboxylate, which was recrystallized from MeOH as a white solid to give 15g, based on 3-pendoxobutanoic acid The yield of benzyl ester was 65%. ¹ H NMR (400 MHz, CDCl ₃ ): 8.88 (br, s, 1H, NH), 7.47-7.33 (m, 5H, C=CH), 5.29 (s, 2H, CH ₂ ), 2.53, 2.48 (2s, 6H, _2CH3 ), 1.56 (s, 9H, 3CH3 ₎ .

Next, in a 25 mL vial, a mixture of 1 g (4.36 mmol) of benzyl 2,4-dimethyl- 1H -pyrrole-3-carboxylate, 0.524 g (4.36 mmol) of MgSO was dissolved in ₈ mL of dry water DCE and stirred at room temperature for 15 minutes in the presence of argon. 0.327 g of 2,6-dimethyl 4-hydroxybenzoic acid (2.18 mmol) was added in small portions; finally closed with a Teflon cap. The resulting mixture was purged with argon for an additional 15 minutes, and TFA (3 drops, catalytic amount) was added. The reaction mixture was stirred at 65°C for 16 hours. TLC and LCMS showed that the starting material had been consumed. To the crude product was added 0.544 g (2.398 mmol) of DDQ in one portion. The resulting mixture was stirred at room temperature for ½ hour. TLC and LCMS showed that the starting material had been consumed. The resulting mixture was filtered through short path celite; the filtrate was concentrated to dryness, the residue was redissolved in 50 mL DCE, stirred with trimethylamine (1.4 mL, 19 mmol) at room temperature for 15 minutes, then cooled to 0 °C. Slowly add 3 mL of BF ₃ . _OEt2 (18.36 mmol). The resulting mixture was stirred at room temperature for ½ hour, then heated to 86°C for 45 minutes. The reaction mixture was then diluted with 150 mL of _CHCl3 and quenched with 50 mL of brine. The organic layer was separated and dried over _MgSO4 , the solvent was removed and rotary evaporated. The residue was chromatographed on a silica gel column using _CH2Cl2 /EtOAc as eluent to give ₁ g of pure 5,5-difluoro-10-(4-hydroxy-2,6-dimethylphenyl) -1,3,7,9-Tetramethyl-5H-414,514-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborin-2 , 8-dicarboxylate dibenzyl ester), compound 5.1, was an orange-red solid in 72% yield based on 2,6-dimethyl 4-hydroxybenzaldehyde. LCMS ( _{APCI- )} , _calcd for M- for _{C37H35BF2N2O5} : _636.26 ; found: 636. ¹ H NMR (400 MHz, chloroform- d ) δ 7.42-7.28 (m, 4H), 6.66 (d, J = 0.7 Hz, 1H), 5.29 (d, J = 11.3 Hz, 2H), 2.82 (s, 3H) , 2.04(d, J = 5.4Hz, 3H), 1.72(s, 3H).

PLC-5: (10-(4-((5-(4,7-bis(4-(diphenylamino)phenyl)-2H-benzo[d][1,2,3]triazole -2-yl)pentanoyl)oxy)-2,6-dimethylphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrole and [1,2-c:2',1'-f][1,3,2]diazaborin-2,8-dicarboxylate dibenzyl ester): from compound 2.1 (0.050 mmol, 32 mg ) and compound 5.1 (0.060 mmol, 42 mg) PLC-5 was prepared in a manner similar to compound 2. by flash chromatography on silica gel (100% hexane (1 CV)→50% DCM/hexane (0 CV)→100% DCM (6 CV)→10% EtOAc/DCM (10 CV)) The crude product was purified. The product containing fractions were evaporated to dryness to give 43 mg of PLC-5 (65% yield). MS (APCI): Calculated for _{formula C84H72BF2N7O6 (} M-) = _{1323 ;} found: 1323. ¹ H NMR (400MHz, chloroform-d) δ 8.00(d, J=8.7Hz, 4H), 7.61(s, 2H), 7.39-7.26(m, 17H), 7.23-7.15(m, 13H), 7.07- 7.02(m, 4H), 6.90(s, 2H), 5.26(s, 4H), 4.86(t, J=7.0Hz, 2H), 2.82(s, 6H), 2.65(t, J=7.3Hz, 2H) ), 2.32(p, J=7.6, 7.1Hz, 2H), 2.06(s, 6H), 1.86(p, J=7.2Hz, 2H), 1.67(s, 6H).

Example 2.6: PLC-6

Compound 6.1.1 4-(4-(4,7-bis(4-(diphenylamino)phenyl)-2H-benzo[d][1,2,3]triazol-2-yl) Phenyl) butyrate methyl ester

Step 1: 4,7-Dibromo-2H-benzo[d][1,2,3]triazole: To 42 mL of stirring deionized aqueous solution was added 2.85 g (41.4 mmol, 1.1 equiv) of sodium nitrite. The solution was then slowly added to 42 mL of cooled glacial acetic acid. After mixing for about 10 minutes, 10 g (37.6 mmol, 1 equiv.) of 3,6-dibromobenzene-1,2-diamine was added. After the addition was complete, the cooling bath was removed. After stirring at room temperature for about 2 hours, the solution was filtered. The collected precipitate was then dried in a room temperature vacuum oven overnight. The desired product was obtained as a beige powder (9.3 g, 89% yield).

Step 2. 4,4'-(2H-benzo[d][1,2,3]triazole-4,7-diyl)bis(N,N-diphenylaniline): under argon 2 g (7.2 mmol, 1 equiv.) of 4,7-dibromo-2H-benzo[d][1,2,3]triazole was added to the condenser's 2-necked flask. 10 mL of n-butanol, 3 mL of toluene and 3 mL of water were added. The mixture was heated to 45°C (while bubbling) for 30 minutes. 5.22 g (18 mmol, 2.50 equiv) of (4-(diphenylamino)phenyl)boronic acid was added followed by 9.19 g (87 mmol, 12 equiv) potassium carbonate. The solution temperature was raised to 110°C. Then 1.67 g (0.144 mmol, 0.2 equiv) of tetrakis(triphenylphosphine)palladium(0) was added. A total of 5 g of additional boric acid, 2 g of base and 0.5 g of catalyst were added. After about 4.5 hours, the reaction was cooled. The reaction was poured into 200 mL of methanol. After stirring for a few minutes, a precipitate precipitated out. Column chromatography was performed using hexane:ethyl acetate (9:1). The desired product was obtained as a bright orange-yellow powder (1.74 g, 40% yield).

Step 3: 4-(4-(4,7-Bis(4-(diphenylamino)phenyl)-2H-benzo[d][1,2,3]triazol-2-yl)benzene yl)butyrate: To a 2-neck flask equipped with a condenser under argon was added 150 mg (583 mmol, 1 equiv) of 4,4'-(2H-benzo[d][1,2 from the previous step ,3]Triazole-4,7-diyl)bis(N,N-diphenylaniline). Subsequently, 2 mL of anhydrous toluene was added, followed by 248 mg (1.2 mmol, 2 equiv.) of potassium phosphate. In a separate vial under argon, add 44 mg (53 μmol, 0.1 equiv) of paras(dibenzylideneacetone)dipalladium(0) and 55 mg (117 μmol, 0.2 equiv) di-tert-butyl (2',4', 6'-Triisopropyl-3,4,5,6-tetramethyl-[1,1'-biphenyl]-2-yl)phosphine. The vial was purged with argon for 15 minutes. Then 2 mL of dry toluene was added. The flask was heated at 120°C for 3 minutes. The first flask was placed in a 120°C heating block. The contents of the vial with ligand and catalyst were then transferred to the flask. After reacting for about 2 hours, the reaction was cooled. Column chromatography was performed using a hexane:ethyl acetate (9:1) gradient. The desired product, compound 6.1.1, was obtained as an orange powder (120 mg, 26%). ¹ H NMR (400MHz, TCE-d2)δ 8.25(d, 2H), 8.04(d, 4H), 7.61(s, 2H), 7.24(m, 10H), 7.14(m, 12H), 7.01(t, 4H), 3.59 (s, 1H), 2.67 (t, 2H), 2.28 (t, 2H), 1.91 (p, 2H).

Compound 6.1 (4-(4-(4,7-bis(4-(diphenylamino)phenyl)-2H-benzo[d][1,2,3]triazol-2-yl)benzene yl)butyric acid): A 100 mL 2-neck round bottom flask was charged with 4-(4-(4,7-bis(4-(diphenylamino)phenyl)-2H-benzo[d][ 1,2,3]Triazol-2-yl)phenyl)butyric acid methyl ester (compound 6.1.1, 0.179 mmol, 140 mg), and the flask was suspended in absolute ethanol (80 mL). The flask was fitted with a finned reflux condenser and flushed with argon. The reaction mixture was treated with potassium hydroxide (12.7 mmol, 713 mg) and heated to 90°C and stirred at this temperature for 6 hours under argon. The reaction was cooled to room temperature, and the reaction mixture was evaporated to dryness. The crude precipitate was isolated in quantitative yield to give compound 6.1 which was used in the next step without further purification. MS (APCI): Calculated for C ₅₂ H ₄₁ N ₅ O ₂ (MH) = 765, found: 765.

PLC-6 (10-(4-((4-(4-(4,7-bis(4-(diphenylamino)phenyl)-2H-benzo[d][1,2,3] Triazol-2-yl)phenyl)butyryl)oxy)-2,6-dimethylphenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4l4,5l4 - Dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaboridine-2,8-dicarboxylate dibenzyl ester): in 40 mL screw cap vials A stir bar was charged, compound 5.1 (0.055 mmol, 35 mg), compound 6.1 (0.050 mmol, 38 mg), and DMAP:pTsOH 1:1 salt (0.200 mmol, 59 mg). The vial was flushed with argon and dry dichloromethane (20 mL) was added. Diisopropylcarbodiimide (0.300 mmol, 47 μL) was added, and the reaction was stirred at room temperature overnight under argon. The next morning, dry tetrahydrofuran (10 mL) was added and sonicated for 30 seconds. An additional portion of compound 6.1 was added and stirred overnight at 50°C under argon. The crude product was purified by flash chromatography on silica gel (60% DCM/hexane (1 CV)→100% DCM (5 CV)→100% DCM (isocratic)). Fractions containing product were evaporated to dryness to give 57 mg of PLC-6 (83% yield). MS (APCI): Calculated for _{C89H74BF2N7O6 ( M-} ) = _{1385 ;} found: 1385. ¹ H NMR (400 MHz, tetrachloroethane- d ₂ ) δ 8.41-8.37 (m, 2H), 8.18-8.12 (m, 4H), 7.71 (s, 2H), 7.43 (d, J =8.5Hz, 2H ),7.41-7.29(m,18H),7.28-7.20(m,12H),7.13-7.06(m,4H),6.97(s,2H),5.27(s,4H),2.89-2.80(m,8H ), 2.64(t, J =7.5Hz, 2H), 2.17-2.09(m, 8H), 1.71(s, 6H).

Example 2.7: PLC-7

Compound 7.1 (5,5-Difluoro-10-(4-hydroxy-2,6-dimethylphenyl)-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[ 1,2-c: 2',1'-f][1,3,2]diazaborin-2,8-dicarbonitrile):

Compound 7.1.1 (cyano-2,4-dimethylpyrrole):

Step 1 : 7.6 mL of 25% HBr/AcOH was slowly added to 19.76 g of solid N -Boc-Gly- N' -methoxy- N' -formamide (90.4 mmol). The solution was stirred at room temperature for 45 minutes. Next, 200 mL of diethyl ether was added to the solution to obtain a white precipitate. The precipitate was filtered to give 18.03 g of glycine N' -methoxy- N' -formamide hydrobromide in 100% yield. LCMS (M+H): 119. ¹ H NMR (DMSO-d6) δ 8.04(3H,s), 3.9(s,2H), 3.72(s,3H), 3.17(s,3H).

Step 2: A solution containing 14.85 g of 3-aminocrotononitrile (180.8 mmol) and 17.95 g of glycine N' -methoxy- N' -methylamide hydrobromide dissolved in 1 L of dry ethanol (90.4 mmol) solution was stirred at room temperature for 16 hours. The resulting solution was concentrated in vacuo to a volume of 50 mL. The solid residue was washed with 40 mL of cold EtOH to give 16.71 g of a white solid. This solid was used in step 3 without further purification. LCMS (M+H) 184. ¹ H NMR(DMSO-δ6) δ 6.9(br,1H), 3.89(s,2H), 3.78(s,1H), 3.7(s,3H), 3.12(s,3H), 2.03(s,3H)

Step 3: To a solution containing 3.82 g of the white powder from Step 2 (21.2 mmol) in 150 mL of dry THF was added 7.5 mL of a 3.0 M solution of MeMgBr in Et ₂ O ( 1.1 equivalents). The solution was stirred for 50 minutes. Next, 15 mL of a 3.0 M solution of MeMgBr in Et ₂ O (2.1 equiv) was added at -10°C under nitrogen atmosphere and stirred for an additional 2 hours. After this time, the solution was quenched with 200 mL of water and extracted with AcOEt. The organic layer was washed with brine and dried _{over Na2SO4} . Filtered and evaporated in vacuo. The product was a yellow solid, which was used in step 4 without further purification.

Step 4: To a slurry containing 2.67 g of the yellow solid from Step 3 (19.3 mmol) in 75 mL of EtOH was added 273 mg of NaOEt (4.01 mmol, 0.2 equiv). The slurry was stirred at room temperature for 30 minutes. Next, the solution was evaporated in vacuo and the residue was dissolved in 100 mL of water and extracted with AcOEt. The organic layer was washed with brine and dried over _MgSO4 . Filtered, evaporated in vacuo, and purified the filtrate by silica gel flash chromatography (n-hexane:AcOEt 3:1 as eluent). 2.09 g (90%) of 3-cyano-2,4-dimethylpyrrole, compound 7.1.1, was obtained as a white solid. LCMS (APCI+): _calcd for _C7H9N2 (M ₊ H) = 121; found: 121. ¹ H NMR(CDCl3) δ 8.06(bs,1H), 6.37(1H,s), 2.37(s,3H), 2.13(s,3H)), 3.74(1H,s), 2.10(3H,s) , 2.02(3H,s).

Compound 7.1.2 ((Z)-5-((4-cyano-3,5-dimethyl-2H-pyrrole-2-ylidene)-(4-hydroxy-2,6-dimethylphenyl )methyl)-2,4-dimethyl-1H-pyrrole-3-carbonitrile) was synthesized using a two (2) step procedure: Step 1: Under argon atmosphere, 1.12 g of 4-hydroxy-2, 6-Dimethylbenzaldehyde (7.49 mmol) was dissolved in 85 mL of dichloromethane/EtOH (9:1). 1.8 g of 2,4-dimethyl-1H-pyrrole-3-carbonitrile (compound 7.1.1, 14.98 mmol) was added. Next, the solution was purged with nitrogen for 30 minutes and TFA (5 drops) was added. The reaction mixture was stirred at room temperature for 16 hours. TFA and solvent were removed under reduced pressure. The crude product was used in step 2 without further purification. LCMS (M+H=373).

Step 2: 8 g of DDQ (35.2 mmol) was added to a solution containing the crude product of Step 1 dissolved in 50 mL of CHCl ₃ and 5 mL of EtOH. The solution was stirred at room temperature for 1 hour. The solvent was removed under reduced pressure. The dark residue was redissolved in 50 mL of _CHCl3 via a short column of silica gel using _CH2Cl2 /EtOAc ( ₁ :1) as eluent to give 2.35 g of compound 7.1.2 as an off-white solid. The overall yield for both steps was 85%. LCMS (APCI+): calcd for _C23H23N4O (M ₊ H) = ₃₇₁ ; found: 371.

Compound 7.1 (5,5-Difluoro-10-(4-hydroxy-2,6-dimethylphenyl)-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[ 1,2-c: 2',1'-f][1,3,2]diazaboridine-2,8-dicarbonitrile): To 50 mL of dry toluene containing 2.35 g of compound 15.2[( Z)-5-((4-cyano-3,5-dimethyl-2H-pyrrole-2-ylidene)-(4-hydroxy-2,6-dimethylphenyl)methyl)-2 ,4-dimethyl-1H-pyrrole-3-carbonitrile] (6.38 mmol) was added 8 mL of triethylamine (52.2 mmol) followed by 10 mL of BF ₃ -etherate (81 mmol). The solution was stirred at room temperature for 16 hours and then heated at 80°C for 1 hour. Next, the solution was cooled to room temperature, and 25 mL of aqueous NaOH (1 M) was added to form an aqueous layer, which was separated. The aqueous layer was neutralized with 4N aqueous HCl, then extracted with EtOAc. The combined organic layers were dried over _MgSO4 and the solvent was removed. The residue was chromatographed on a silica gel column using hexane/EtOAc (1:1) as eluent to give 1.05 g of product (39% yield). LCMS (APCI ₊ ): _calcd for _C23H22BF2N4O (M ₊ H) = 419; found: 419. ¹ H NMR (400 MHz, chloroform- d ) δ 6.73 (s, 2H), 2.73 (s, 6H), 2.05 (s, 6H), 1.64 (s, 6H).

PLC-7 (4-(4-(4,7-bis(4-(diphenylamino)phenyl)-2H-benzo[d][1,2,3]triazol-2-yl) Phenyl)butanoic acid 4-(2,8-dicyano-5,5-difluoro-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c : 2',1'-f][1,3,2]diazaborane-10-yl)-3,5-dimethylphenyl ester): A 40 mL screw cap vial was charged with a stir bar, compound 7.1 (0.055 mmol, 35 mg) and compound 6.1 (0.050 mmol, 38 mg), and DMAP:pTsOH 1:1 salt (0.200 mmol, 59 mg). The vial was flushed with argon and dry dichloromethane (20 mL) was added. Diisopropylcarbodiimide (0.300 mmol, 47 uL) was added and the reaction was stirred overnight at room temperature under argon. The next morning, dry tetrahydrofuran (10 mL) was added and sonicated for 30 seconds. Another portion of compound 2.1 was added and stirred overnight at 50°C under argon. The crude product was purified by flash chromatography on silica gel (80% DCM/hexane (1 CV)→100% DCM (5 CV)→100% DCM (isocratic)). Fractions containing product were evaporated to dryness to give 21 mg of PLC-7 (36% yield). MS (APCI): Calculated for formula C ₇₅ H ₆₀ BF ₂ N ₉ O ₂ (M-) = 1167; found: 1167.

Example 2.8: PLC-8

Compound 8.1 (4,7-Dibromo-2-(4-fluorophenyl)-2H-benzo[d][1,2,3]triazole):

Step 1: Potassium monopersulfate (78.88 g, 127.96 mmol) was added to a mixture of 2-nitroaniline (10.58 g, 76 mmol) in _H2O (210 mL), DCM (590 mL), and the The resulting mixture was stirred at 40°C for 48 hours. After cooling to room temperature, the reaction was isolated. The aqueous layer was re-extracted with DCM (150 mL x 2), the DCM layers were combined, washed with IN aq. HCl, water and brine, then dried over _MgSO4 , and concentrated to dryness. The brown solid was pulverized with EtOH, filtered, and air dried to yield 6.61 g of product as a light brown solid. The yield was 57%. The product was used in the next step without further purification. LCMS (APCI+): Calculated for _{M +} of _{formula C6H4N2O3} : 152.11; found: 152

Step 2: A mixture of 1-nitro-2-nitrosobenzene (1.4 g, 9.2 mmol), 4-fluoroaniline (1.02 g, 9.2 mmol) in AcOH (50 mL) was stirred at room temperature for 16 hours. The mixture was poured into ice water, the brown solid was collected by filtration, the product was washed several times with water, and then dried in a vacuum oven to dryness to yield 2.0 g of the product as a light brown solid. The yield was 89%. The product was used in the next step without further purification. LCMS (APCI+): Calculated for _M + of _{formula C12H8FN3O2} : _245.21 ; found: 245.

Step 3: Formamidine sulfinic acid (2.9 g, 26.89 mmol) was added to (E/Z)-1-(4-fluorophenyl)-2-(2-nitrophenyl)diazene (2.0 g , 8.15 mmol) in EtOH (50 mL), followed by the addition of 4N aqueous NaOH (42 mL), and the resulting mixture was stirred at 85 °C for 16 h. After cooling to room temperature, the solution was poured into ice water, the brown solid was collected by filtration, the product was washed several times with water, and then dried to dryness in a vacuum oven to yield 1.61 g of the product as a light brown solid. Yield was 93%. The product was used in the next step without further purification. LCMS (APCI+): Calculated for _M + of formula _C12H8FN3 : _213.22 ; found: 213. ¹ H NMR (400MHz, CDCl3): 8.33 (d, J=9.16 Hz, 2H), 7.92 (d, J=9.5 Hz, 2H), 7.42 (d, J=9.9 Hz, 2H), 7.24 (d, J =2.92Hz,2H),

Step 4: Bromine (0.93 mL, 18.16 mmol) was added dropwise to 2-(4-fluorophenyl)-2H-benzo[d][1,2,3]triazole (1.55 g, 7.26 mmol) at 48 % HBr (20 mL), the resulting mixture was stirred at 130 °C for 16 h. After cooling to room temperature, the solution was decanted and discarded; the remainder of the flask was added to ice water and the product was extracted into ethyl acetate:THF (1:1). The organic layer was separated, dried over _MgSO4 , and concentrated. The filtrate was concentrated to dryness. The crude product was purified by _SiO2 column chromatography, eluted with hexane:ethyl acetate (95:5) to give 1.96 g of compound 8.1. The yield was 73%. LCMS (APCI+): Calculated for _M + of _{formula C12H6Br2FN3} : _371.01 ; found: 371. ¹ H NMR (400MHz, CDCl3): 8.41 (d, J=9.2Hz, 2H), 7.47 (s, 2H)), 7.52 (dd, J=10.1Hz, 2Hz, 2H)

Compound 8.2 (4,4'-(2-(4-fluorophenyl)-2H-benzo[d][1,2,3]triazole-4,7-diyl)bis(N,N-diyl) Phenylaniline) : A 250 mL 2-neck round-bottomed flask was charged with a stir bar and equipped with a finned condenser and gas adapter. The flask was flushed with argon. Compound 8.1[4,7-dibromo was added to the flask -2-(4-Fluorophenyl)-2H-benzo[d][1,2,3]triazole] (3.14 mmol, 1.165 g), n-butanol (20 mL), toluene (6 mL) and water ( 6 mL). The flask was heated to 45°C in a heating block and bubbled with argon for 30 minutes. Then (4-(diphenylamino)phenyl)boronic acid (13.8 mmol) was added while sparging with argon. , 3.994 g), sodium carbonate (37.68 mmol, 3.994 g) and Pd(PPh ₃ ) ₄ (0.628 mmol, 726 mg). Stopper the flask and raise the heating block temperature to 110° C. under argon atmosphere. Stir and Heated at this temperature overnight. The reaction mixture was worked up and purified by flash chromatography on silica gel (100% hexanes (1 CV)→30% toluene/hexanes (0 CV)→100% toluene (10 CV) ) purification. The fractions containing the product were evaporated to dryness to give 546 mg of compound 8.2 (25% yield). MS (APCI): Calculated for C ₄₈ H ₃₄ FN ₅ (M-) = 699; found : 699.

Compound 8.3 (4-(4-((4-(7-(4-(diphenylamino)phenyl)-2-(4-fluorophenyl)-2H-benzo[d][1,2 ,3]Triazol-4-yl)phenyl)(phenyl)amino)phenyl)-4-oxybutyric acid methyl ester): A 250 mL 2-neck round bottom flask was charged with a stir bar, and Fitted with finned condenser and gas adapter. The flask was flushed with argon. To this flask were added compound 8.2 (0.780 mmol, 546 mg), anhydrous dichloromethane (100 mL), ZnCl ₂ (1.0 M in Et ₂ O, 2.34 mmol, 2.34 mL) followed by 4-chloro-4 with stirring - Methyl oxybutyrate (2.34 mmol, 0.288 mL). The reaction was stirred at room temperature under argon for 30 minutes, then heated to 45°C overnight. Diethyl ether and dichloromethane were evaporated under a stream of argon and replaced with dichloroethane (100 mL). The flask was stoppered and heated at 55°C for 1 hour, then 65°C for 3 hours. Additional methyl 4-chloro-4-pentoxybutyrate (2.34 mmol, 0.288 mL) was added and heating at 65°C continued for 7 hours. The reaction mixture was cooled to room temperature, evaporated to dryness, and purified by flash chromatography on silica gel (100% DCM (1 CV)→10% EtOAc/DCM (10 CV)). The fractions containing the product were evaporated to dryness to give 160 mg of compound 8.3 (25% yield). MS (APCI): Calculated for formula C ₅₃ H ₄₀ FN ₅ O ₃ (M-) = 813; found: 813.

Compound 8.4 (4-(4-((4-(7-(4-(diphenylamino)phenyl)-2-(4-fluorophenyl)-2H-benzo[d][1,2 ,3]Triazol-4-yl)phenyl)(phenyl)amino)phenyl)butyric acid methyl ester): A 40 mL screw cap vial was charged with compound 8.3 (0.197 mmol, 160 mg) and a stir bar . The vial was flushed with argon. To the vial was added anhydrous dichloromethane (10 mL) and trifluoroacetic acid (10 mL). The vial was sealed with a screw cap septum and triethylsilane (6.6 mmol, 1.05 mL) was added with stirring. The reaction was stirred at room temperature under argon for 4 hours, at which time the reduction was found to be complete by LCMS. The reaction mixture was evaporated to dryness and azeotroped with toluene to remove residual trifluoroacetic acid. Triethylsilane was added several times until LCMS showed no more starting material. The crude reaction mixture was evaporated to dryness and purified by flash chromatography on silica gel (100% DCM isocratic). Fractions containing the product were evaporated to dryness to give 140 mg of compound 8.4 (89% yield). MS (APCI): Calculated for formula C ₅₃ H ₄₂ FN ₅ O ₂ (M-) = 799; found: 799.

Compound 8.5 (4-(4-((4-(7-(4-(diphenylamino)phenyl)-2-(4-fluorophenyl)-2H-benzo[d][1,2 , 3] Triazol-4-yl)phenyl)(phenyl)amino)phenyl)butyric acid) : A 250 mL 2-neck round bottom flask was charged with a stir bar and equipped with a finned condenser and Gas adapter. The flask was flushed with argon. To the flask was added compound 8.4 (0.174 mmol, 139 mg) followed by n-butanol (100 mL) followed by KOH (5.0 M in water, 1.740 mmol, 0.350 mL). The flask was stoppered and heated in a heating block with stirring at 115 °C overnight under argon. The reaction mixture was cooled to room temperature and water (10 mL) was added. Trifluoroacetic acid was added until pH was about 1. The reaction was evaporated to dryness. The fraction soluble in dichloromethane was evaporated to dryness to give compound 8.5 in quantitative yield. MS (APCI): Calculated for C ₅₂ H ₄₀ FN ₅ O ₂ (MH) = 784, found: 784.

PLC-8 (10-(4-((4-(4-((4-(7-(4-(diphenylamino)phenyl)-2-(4-fluorophenyl)-2H-benzene [d][1,2,3]triazol-4-yl)phenyl)(phenyl)amino)phenyl)butyryl)oxy)-2,6-dimethylphenyl)-5,5 -Difluoro-1,3,7,9-tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazepine dibenzyl borazol-2,8-dicarboxylate): A 250 mL 2-neck round bottom flask was equipped with a finned condenser, stir bar, and gas adapter. The flask was flushed with argon, and compound 8.5 (0.050 mmol, 39 mg) and compound 5.1 (0.055 mmol, 35 mg), and DMAP:pTsOH 1:1 salt (0.200 mmol, 59 mg) were added. The vial was flushed with argon and dry dichloromethane (20 mL) was added. Diisopropylcarbodiimide (0.300 mmol, 47 uL) was added and the reaction was stirred overnight at room temperature under argon. The crude product was purified by flash chromatography on silica gel (80% DCM/hexane (1 CV)→100% DCM (5 CV)→100% DCM (isocratic)). The fractions containing the product were evaporated to give 63 mg of PLC-8 (90% yield). MS (APCI): Calculated for formula C ₈₉ H ₇₃ BF ₃ N ₇ O ₆ (M-) = 1403; found: 1403. ¹ H NMR (400 MHz, tetrachloroethane- d ₂ ) δ 8.41-8.37 (m, 2H), 8.15 (d, J=8.8 Hz, 4H), 7.71 (s, 2H), 7.46-7.30 (m, 20H ),7.28-7.19(m,11H),7.13-7.06(m,4H),6.97(s,2H),5.27(s,4H),2.90-2.81(m,8H),2.64(t,J=7.5 Hz, 2H), 2.17-2.09 (m, 8H), 1.71 (s, 6H).

Example 2.9: PLC-9

PLC-9 (4-(4-((4-(7-(4-(diphenylamino)phenyl)-2-(4-fluorophenyl)-2H-benzo[d][1, 2,3]Triazol-4-yl)phenyl)(phenyl)amino)phenyl)butyric acid 4-(2,8-dicyano-5,5-difluoro-1,3,7, 9-Tetramethyl-5H-4l4,5l4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaboran-10 -yl)-3,5 - dimethylphenyl ester): A 250 mL 2-neck round bottom flask was fitted with a finned condenser, stir bar and gas adapter. The flask was flushed with argon and compound 7.1 (0.055 mmol, 35 mg) and compound 8.5 (0.050 mmol, 39 mg), and DMAP:pTsOH 1:1 salt (0.200 mmol, 59 mg) were added. The vial was flushed with argon and dry dichloromethane (20 mL) was added. Diisopropylcarbodiimide (0.300 mmol, 47 uL) was added and the reaction was stirred overnight at room temperature under argon. The crude product was purified by flash chromatography on silica gel (80% DCM/hexane (1 CV)→100% DCM (5 CV)→100% DCM (isocratic)). Fractions containing product were evaporated to dryness to give 39 mg (59% yield). MS (APCI): Calculated for _{C75H59BF3N9O2 ( M-} ) _{= 1185} ; found: 1185. ¹ H NMR (400 MHz, tetrachloroethane- d ₂ ) δ 8.48-8.42 (m, 2H), 8.16-8.11 (m, 4H), 7.71 (s, 2H), 7.37-7.30 (m, 5H), 7.30 -7.19(m, 10H), 7.18(s, 3H), 7.10(td, J =7.1, 1.4Hz, 3H), 7.06(s, 2H), 2.79-2.72(m, 8H), 2.67(t, J =7.5Hz, 2H), 2.13(s, 8H), 1.63(s, 6H).

Example 3 Production of color conversion film

A glass substrate was prepared substantially as follows. A 1.1 mm thick glass substrate measuring 1 inch x 1 inch was cut to size. The glass substrates were then washed with detergent and deionized (DI) water, rinsed with fresh deionized water, and sonicated for about 1 hour. The glass was then immersed in isopropyl alcohol (IPA) and sonicated for about 1 hour. The glass substrates were 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.

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

The 20% PMMA solution prepared above (4 g) was added to 3 mg of the photoluminescent composite prepared above in a sealed container and mixed for about 30 minutes. The PMMA/phosphor solution was then spin-coated onto the prepared glass substrate at 1000 RPM for 20 seconds and then spun at 500 RPM for 5 seconds. The thickness of the resulting wet coating was about 10 μm. Before spin coating, the samples were covered with aluminum foil to prevent exposure of the samples to light. Three samples were prepared in this way for which emission/FWHM and quantum yield were measured, respectively. The spin-coated samples were baked in a vacuum oven at 80°C for 3 hours to evaporate residual solvent. The thickness of the dried coating was about 2 μm.

A 1 inch x 1 inch sample was inserted into a Shimadzu, UV-3600 UV-VIS-NIR spectrophotometer (Shimadzu Instruments, Columbia, MD, USA). All equipment operations were performed in a nitrogen-filled glove box. The resulting absorption/emission spectrum of PLC-1 is shown in Figure 1, while the resulting absorption/emission spectrum of PLC-5 is shown in Figure 2.

The fluorescence spectra of the 1 inch x 1 inch film samples prepared as described above were measured using a Fluorolog spectrofluorometer (Horiba Scientific, Edison, NJ, USA) with the excitation wavelength set to the corresponding maximum absorption wavelength . The maximum emission and FWHM are shown in Table 1.

The quantum yields of 1 inch x 1 inch samples prepared as described above were determined using a Quantarus-QY spectrophotometer (Hamamatsu Corporation, Campbell CA, USA) excited at the corresponding absorption maximum wavelengths . The results are reported in Table 1.

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

Claims (21)

A photoluminescent composite comprising: a blue light absorbing azole derivative; a linking group comprising an unsubstituted ester or a substituted ester, wherein the linking group has a total of The blue light absorbing azole derivative is valently linked to the boron dipyrrole methylene boron (BODIPY) moiety; wherein the blue light absorbing azole derivative is represented by the following chemical formula:

wherein Z is NR ¹⁰ or S; R ⁹ is H or the linking group; and R ¹⁰ is H, substituted aryl, or the linking group; wherein the azole derivative absorbs the first excitation wavelength light energy and transfer energy to the BODIPY moiety, wherein the BODIPY moiety absorbs the energy from the azole derivative and emits a second higher wavelength light energy. The photoluminescent composite of claim 1, wherein the BODIPY moiety has the following general formula:

wherein R ¹ and R ⁶ are independently H, alkyl, alkenyl, alkynyl or alkoxy-3-oxopropen-1-yl; wherein R ³ and R ⁴ are independently H or C ₁ -C ₂ alkane wherein R ² and R ⁵ are independently H, alkyl, alkenyl, alkynyl, -CN, alkyl ester or aryl ester; wherein R ² and R ³ can be linked together to form an additional monocyclic hydrocarbon A ring structure or a polycyclic hydrocarbon ring structure; wherein R ⁴ and R ⁵ can be joined together to form an additional monocyclic hydrocarbon ring structure or a polycyclic hydrocarbon ring structure; wherein R ⁷ and R ⁸ are independently H or methyl; and wherein L is the linking group. The photoluminescent composite of claim 1, wherein the BODIPY moiety has the following general formula:

wherein R ¹ and R ² are joined together to form additional polycyclic hydrocarbon ring structures; wherein R ⁵ and R ⁶ are joined together to form additional polycyclic hydrocarbon ring structures; wherein R ⁷ and R ⁸ are independently H or methyl and wherein L is the linking group. A photoluminescent composite as claimed in claim 1, 2 or 3, wherein Z is S. A photoluminescent complex as claimed in claim 1, 2 or 3, wherein Z is NR ¹⁰ and R ¹⁰ is substituted phenyl. The photoluminescent composite of claim 5, wherein R ¹⁰ is

. The photoluminescent complex of claim 2 or 3, wherein R ⁷ and R ⁸ are methyl groups. The photoluminescent composite of claim 2, wherein R ¹ , R ³ , R ⁴ and R ⁶ are C ₁ -C ₂ alkyl groups. The photoluminescent composite of claim 2, wherein R ¹ , R ³ , R ⁴ and R ⁶ are methyl groups. The photoluminescent composite of claim 2, wherein R ¹ and R ⁶ are:

The photoluminescent complex of claim 1, 2 or 3, wherein the linking group is:

The photoluminescent complex of claim 1, 2 or 3, wherein the linking group is:

The photoluminescent composite of claim 1, wherein the photoluminescent composite is:

A color conversion film, the color conversion film comprising: a transparent substrate layer; a color conversion layer, wherein the color conversion layer comprises a resin matrix; and a photoluminescent composite, wherein the photoluminescent composite A photoluminescent compound of 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 or 13 dispersed within the resin matrix. The color conversion film of claim 14, wherein the color conversion film also includes a singlet oxygen quencher. The color conversion film of claim 14 or 15, wherein the color conversion film also contains free radical scavengers remover. The color conversion film of claim 14 or 15, wherein the thickness of the film is between 1 μm and 200 μm. The color converting film of claim 14 or 15, wherein the film absorbs light in a wavelength range of about 400 nm to about 480 nm and emits light in a wavelength range of about 510 nm to about 560 nm. The color converting film of claim 14 or 15, wherein the film absorbs light in a wavelength range of about 400 nm to about 480 nm and emits light in a wavelength range of about 575 nm to about 645 nm. A backlight unit comprising the color conversion film of claim 14, 15, 16, 17, 18 or 19. A display device comprising a backlight unit as claimed in claim 20.

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