TW202140749A - 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 luminescent compound and color conversion film containing the boron-containing cyclic luminescent compound

The present invention relates to a compound used in a color conversion film, a backlight unit, and a display device including the color conversion film and the backlight unit.

In color reproduction, the color gamut (gamut/color gamut) is a specific complete subset of the colors available on the device (such as a TV or monitor). For example, Adobe ^TM Red, Green, and Blue (RGB) was developed to provide a wider color gamut and provide a more realistic representation of the visible colors viewed by the display. The Adobe TM RGB is a wide range of colors achieved by using pure spectral primary colors. Domain color space. It is believed that devices that can provide a wider color gamut can enable the display to depict more vivid colors.

As high-definition large-screen displays become increasingly popular, the demand for higher-efficiency, thinner, and more powerful displays is also growing. The existing light emitting diode (LED) is obtained by exciting a green phosphor, a red phosphor or a yellow phosphor by a blue light source to obtain a white light source. However, the full width at half maximum (FWHM) of the emission peaks of the existing green phosphors and red phosphors is very large, usually greater than 40 nm, which causes the green spectrum and the red spectrum to overlap and the colors cannot be completely distinguished from each other. Such overlap can lead to poor color reproduction and color gamut degradation.

In order to correct the color gamut degradation, a method using a combination of a film containing quantum dots and an LED has been developed. However, there are problems with the use of quantum dots. First, cadmium-based quantum dots are extremely toxic and are banned in many countries due to health and safety issues. Second, the efficiency of non-cadmium-based quantum dots in converting blue LED light into green and red light is very low. Third, quantum dots require expensive packaging processes to protect against moisture and oxygen. Finally, since it is difficult to control the size uniformity during the production process, the cost of using quantum dots is high.

The photoluminescent composite described herein can be used to improve the contrast between distinguishable colors in televisions, computer monitors, smart devices, and any other devices that utilize color display. The photoluminescence composite of the present invention provides a novel color conversion dye composite, which has good blue light absorbance and narrow emission band width, in which 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 composite disclosed in the present invention can be used as a color conversion film in a light-emitting device. The color conversion film of the present invention reduces the color degradation by reducing the overlap in the chromatogram, thereby producing high-quality color reproduction.

Some embodiments include a photoluminescent composite that includes a blue light-absorbing azole derivative; a linker group (such as a linker group containing an unsubstituted or substituted ester); and two Boron pyrromethene (BODIPY) part. 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 partially absorbs energy from the azole derivative and emits light energy at a second higher wavelength. In some embodiments, the emission quantum yield of the photoluminescent composite is greater than 70%.

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

In some embodiments, the photoluminescent composite may have a Stokes shift equal to or greater than 45 nm, that is, the difference between the excitation peak of the blue absorption part and the emission peak of the BODIPY part.

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

.

In some embodiments, Z may be nitrogen (NR ¹⁰ ). In some embodiments, Z may be sulfur (S). In some embodiments, Z may be oxygen (O). In some embodiments, R ⁹ can be H or a linker (e.g., 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 linking group (for example, an unsubstituted ester linking group or a substituted ester linking 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 may have the following general formula:

; Wherein R ¹ -R ^{8 are} as described in more detail below, and L represents a linking group, for example, a linking group containing an unsubstituted ester or a substituted ester.

Some embodiments include a color conversion film comprising: a color conversion layer, wherein the color conversion layer includes a resin matrix; and the photoluminescent composite described herein, the photoluminescent composite 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 opposite surfaces, and the color conversion layer is disposed on one of the opposite surfaces.

Some embodiments include a method of preparing the color conversion film, the method comprising: dissolving at least one of the aforementioned photoluminescent composites and a binder resin in a solvent; and applying the mixture to opposite surfaces of a transparent substrate. On one surface.

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

Cross-reference of related applications This application claims the rights and interests of U.S. Provisional Application No. 62/992,776 filed on March 20, 2020. The entire content of the U.S. Provisional Application is incorporated herein by reference.

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

As used herein, when a compound or chemical structure is referred to as "substituted," it may contain one or more substituents. The substituted group is derived from the unsubstituted parent structure, wherein one or more hydrogen atoms on the parent structure have been independently substituted by one or more substituents. In one or more forms, the substituents may be independently selected from the optionally substituted alkyl group, an alkenyl group, a ketone, an aryl group or a C ₃ -C ₇ heteroalkyl.

The term "alkyl" group as used herein refers to a hydrocarbyl group without C=C groups or C≡C groups. The "alkenyl" moiety refers to a group with at least one carbon-carbon double bond (-C=C-), and the "alkynyl" moiety refers to a group with at least one carbon-carbon triple bond (-C≡C-) Group. The alkyl, alkenyl, or alkynyl moiety, whether saturated or unsaturated, can be branched, linear or cyclic.

The alkyl moiety can have 1 to 6 carbon atoms (regardless of whether it appears in this document, a numerical range such as "1 to 6" refers to each integer within the given range: for example, "1 to 6 carbon atoms" refers to Refers to the 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 the occurrence of the term "alkyl" without a specified numerical range. Designated herein The alkyl group of the compound can be called "C ₁ -C ₆ alkyl" or similar names. For example only, "C ₁ -C ₆ alkyl" means that there are one to six carbon atoms in the alkyl chain , That is, the alkyl chain is selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, second butyl and tertiary 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 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary 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 has been replaced by nitrogen, oxygen, or sulfur. Examples include but are not limited to -CH ₂ -O-CH ₃ , -CH ₂ -CH ₂ -O-CH ₃ , -CH ₂ -NH-CH ₃ , -CH ₂ -N(CH ₃ )-CH ₃ , -CH ₂ -CH ₂ -NH-CH ₃ , -CH ₂ -CH ₂ -N(CH ₃ )-CH ₃ , -CH ₂ -S-CH ₂ -CH ₃ , -CH ₂ -CH ₂ -S(O)- CH ₃ . In addition, up to two heteroatoms may be continuous, such as, for example, -CH ₂ -NH-O-CH ₃ and the like.

The term "aromatic" refers to a planar ring with a non-localized π electron system containing 4n+2 π electrons, where n is an integer. Aromatic rings can be formed by five, six, seven, eight, nine, or more than nine atoms. Aromatics can be optionally substituted. The term "aromatic" includes carbocyclic aryl (e.g., phenyl) and heterocyclic aryl (or "heteroaryl" or "heteroaromatic") groups (e.g., 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 that contains only carbon and hydrogen and may be saturated. Monocyclic hydrocarbon rings include groups having 3 to 12 carbon atoms. Illustrative examples of monocyclic groups include the following:

Wait. Illustrative examples of polycyclic groups include the following:

[Dicyclooctane],

[Dicyclopentane],

[Dicycloheptane],

[Dicycloheptane],

[Dicyclodecane],

[Decahydronaphthalene],

[Octahydrocyclopentadiene],

[Octahydroindene],

[Hexahydroindene],

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

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

[1,1-Dimethyl-2,3-dihydro-1 H -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 in which every atom forming the ring is a carbon atom. Aromatic rings can be formed by five, six, seven, eight, or more than eight carbon atoms. Aryl groups can be substituted or unsubstituted. Examples of aryl groups include, but are not limited to, phenyl, naphthyl, phenanthryl, and the like.

The term "aralkyl" refers to an alkyl group as defined herein substituted with an aryl group as defined herein. 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 restriction is that the ring of the group does not contain two adjacent oxygen or sulfur atoms. It should be understood that the heteroaromatic ring may have additional heteroatoms in the ring. In a heteroaryl group 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. The 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: pyrrole, imidazole, pyridine, and the like.

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

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

The term "portion" as used herein refers to a specific segment or functional group of a molecule. The 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, where R is selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl (bonded by ring carbon) and heterocycle (bonded by 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 easily found in known reference sources.

The term "ether" as used herein refers to a chemical moiety containing an oxygen atom connected to two alkyl or aryl groups, having the general formula R-O-R', where 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) connected to two alkyl or aryl groups, having the general formula RC(=O)R', where the term alkane Group and aryl are as defined herein.

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

.

。The term "BODIPY" as used herein refers to a chemical moiety with the following formula:

.

The BODIPY moiety may consist of a dipyrromethene group compounded with a disubstituted boron atom (usually a BF _{2 unit).} The IUPAC name of BODIPY core is 4,4-difluoro-4-bora-3a,4a-diaza-s-dicyclopentacene (4,4-difluoro-4-bora-3a,4a- diaza-s-indacene).

The use of the terms "may" or "may be" should be interpreted as "is" or "is not", or alternatively "does" or "and Abbreviations for “does not” or “will” or “will not”. For example, the sentence "The distance between the blue light-absorbing azole derivative and the BODIPY part can be about 8 Å or greater" should be interpreted as, for example, "In some embodiments, the distance between the blue light-absorbing azole derivative and the BODIPY part is about 8 Å or greater", or "in some embodiments, the distance between the blue absorbing azole derivative and the BODIPY portion is not about 8 Å or greater".

The present invention relates to a photoluminescent composite that absorbs light energy at a first wavelength and emits light energy at a second higher wavelength. The photoluminescence composite of the present invention includes an absorbing light-emitting part and an emitting light-emitting part, and the absorbing light-emitting part and the emitting light-emitting part are connected by a connecting base, so that their distance is tuned to absorb the light-emitting part and transfer its energy to the acceptor to emit light. Part, where the light-emitting part of the acceptor subsequently emits at a second wavelength greater than the first wavelength absorbed.

The photoluminescent composite of the present invention comprises: a blue light-absorbing azole derivative; a linking group; and a boron dipyrromethene (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 the light of the first excitation wavelength and transfers the energy to the BODIPY part, and then the BODIPY part emits light energy of a second wavelength, wherein the light energy of the second wavelength is higher than that of the first wavelength. wavelength. It is believed that the energy transfer from the excited azole derivatives to the BODIPY moiety occurs through Forster resonance energy transfer (FRET). This idea is that due to the absorption/emission spectrum of the photoluminescence complex, there are two main absorption bands in the absorption/emission spectrum, one is at the blue absorption band (azole derivatives), and the other is at the BODIPY absorption band, and Only one emission band is located at the emission wavelength of the BODIPY part (see Figure 1 and Figure 2).

In one embodiment, the photoluminescent composite may 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 measured by dividing the number of emitted photons by the number of absorbed photons, and the emission quantum yield is equivalent to the emission efficiency of the light-emitting part. In some embodiments, the emission quantum yield of the absorbing light-emitting part 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%). The quantum yield in the film can be measured by a spectrophotometer, such as a Quantaurus-QY spectrophotometer (Humamatsu, Campbell, CA, USA).

In some embodiments, the photoluminescent composite has an emission band, which may have a full width at half maximum (FWHM) less than 40 nm. FWHM is the width in nanometers of the emission band at half the maximum emission intensity of the band. In some embodiments, the photoluminescent composite has an emission band FWHM value 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 may 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 absorption part and the emission peak of the BODIPY part.

The photoluminescent composite of the present invention can have a tunable emission wavelength. The different substitution types on the BODIPY part can tune the emission wavelength (for example, the maximum emission wavelength or the peak emission wavelength) to be between 510 nm and about 560 nm, or between about 610 nm and about 645 nm, or here Any wavelength within the range defined by any of the equivalent values.

In some embodiments, the blue absorbing portion may have a peak absorption maximum between about 400 nm and about 470 nm wavelength. In some embodiments, the peak absorption may 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 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, about 460 nm to about 465 nm, about 465 nm to about 470 nm, or any wavelength within the range defined by any of these equivalent values.

In some embodiments, the photoluminescent composite may 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 Between, about 535 nm to about 540 nm, about 540 nm to about 545 nm, about 545 nm to about 550 nm, about 550 nm to about 555 nm, about 555 nm to about 560 nm, or equivalent Any wavelength within the range defined by any value in.

In another embodiment, the photoluminescent composite 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, Between about 635 nm and about 640 nm, between about 640 nm and about 645 nm, or any wavelength within the range defined by any of these equivalent values.

Other embodiments include photoluminescent composites, in which the spatial distance between the blue light-absorbing azole derivative and the BODIPY moiety is adjusted by a linking group, so as to transfer the energy of the blue light-absorbing azole derivative to the BODIPY moiety.

The present invention describes a photoluminescent composite, wherein the photoluminescent composite may include a blue light-absorbing azole derivative, a linking group and a BODIPY moiety. The linking group covalently connects the blue light-absorbing azole derivative and the BODIPY moiety. In some embodiments, the azole derivative absorbs light energy at a first excitation wavelength and transfers the energy to the BODIPY portion, wherein the BODIPY portion 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 composite 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 following general formula:

, Where Z can be selected from NR ¹⁰ , S or O; R ⁹ is H or a substituted ester linker; and R ¹⁰ is H, a substituted aryl group, or a substituted ester linker.

。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, for example

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

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

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

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

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

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

.

The linking group covalently connects the blue light-absorbing azole derivative and the BODIPY moiety. The linking group can be changed to adjust the spatial 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 linking group, such as L, may include a substituted ester linking group. The substituted ester linker may include one of the following structures:

.

。Alternatively, the linking group, such as L, may include an unsubstituted ester linking group. The unsubstituted ester linking group may include 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 composite of the present invention may include a BODIPY moiety. The BODIPY part can have the following general formula:

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

; In some embodiments, R ¹ is methoxy-3-oxypropen-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-oxypropen-1-yl. For R ^1-alkoxy-3 oxo - propen-1-yl ester, also contemplated other alkoxy groups. R ⁶ may be H, alkyl, alkenyl, alkynyl, or alkoxy-3-oxypropen-1-yl. In some embodiments, R ⁶ is H. In some embodiments, R ⁶ is an alkyl group, such as a C _1-6 alkyl group (e.g., methyl, ethyl, propyl, isopropyl, C ₄ alkyl, C ₅ alkyl, or C ₆ alkyl). In some embodiments, R ⁶ is alkenyl, such as C _2-6 alkenyl (e.g., 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-oxypropen-1-yl, such as methoxy-3-oxypropen-1-yl, ethoxy-3-oxypropen-1-yl, propenyl Oxy-3-oxypropene-1-yl and the like. In some embodiments, R ⁶ is ethoxy-3-oxypropen-1-yl.

R ³ may be H or an alkyl group, such as a C _1-6 alkyl group or a C ₁ -C ₂ alkyl group. 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 may be H or an alkyl group, such as a C _1-6 alkyl group or a C ₁ -C ₂ alkyl group. 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.

R ² can be H, alkyl, alkenyl, alkynyl, -CN, alkyl ester (for example, -C(O)OCH ₂ CH ₃ ), or aryl ester (for example, -COOCH ₂ Ar). In some embodiments, R ² is H. In some embodiments, R ² is an alkyl group, such as a C _1-6 alkyl group (e.g., methyl, ethyl, propyl, isopropyl, C ₄ alkyl, C ₅ alkyl, or C ₆ alkyl). In some embodiments, R ² is alkenyl, such as C _2-6 alkenyl (e.g., vinyl, propenyl, C ₄ alkenyl, C ₅ alkenyl, C ₆ alkenyl). In some embodiments, R ² is alkynyl, such as 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).

R ⁵ may be H, alkyl, alkenyl, alkynyl, -CN, alkyl ester (for example, -C(O)OCH ₂ CH ₃ ), or aryl ester (for example, -COOCH ₂ Ar). In some embodiments, R ⁵ is H. In some embodiments, R ⁵ is an alkyl group, such as a C _1-6 alkyl group (e.g., methyl, ethyl, propyl, isopropyl, C ₄ alkyl, C ₅ alkyl, or C ₆ alkyl). In some embodiments, R ⁵ is alkenyl, such as C _2-6 alkenyl (e.g., vinyl, propenyl, C ₄ alkenyl, C ₅ alkenyl, C ₆ alkenyl). In some embodiments, R ⁵ is alkynyl, such as 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 (e.g., -COOCH ₂ Ar).

R ² and R ³ may be connected together to form another monocyclic hydrocarbon ring structure or polycyclic hydrocarbon ring structure;

R ⁴ and R ⁵ may be connected together to form another monocyclic hydrocarbon ring structure or polycyclic hydrocarbon ring structure;

R ⁷ may be H or an alkyl group, such as a C _1-6 alkyl group (e.g., a methyl group, an ethyl group, a propyl group, an isopropyl group, a C ₄ alkyl group, a C ₅ alkyl group, or a C ₆ alkyl group). In some embodiments, R ⁷ is H. In some embodiments, R ⁷ is methyl (-CH ₃ ).

R ⁸ may be H or an alkyl group, such as a C _1-6 alkyl group (e.g., methyl, ethyl, propyl, isopropyl, C ₄ alkyl, C ₅ alkyl, or C ₆ alkyl). In some embodiments, R ⁸ is H. In some embodiments, R ⁸ is methyl (-CH ₃ ).

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

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

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

.

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

In some embodiments, the BODIPY portion of the present invention may be the following BODIPY portion, wherein R ¹ , R ³ , R ⁴ and R ⁶ are each a methyl group; R ² and R ⁵ are both substituted ester groups, wherein the The substituted ester group contains an alkyl chain; R ⁷ and R ⁸ are each a methyl group; and L contains a linking group.

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

In some embodiments, the BODIPY portion of the present invention may include the following BODIPY portion, wherein R ¹ and R ⁶ may be alkenyl groups, R ² and R ^{3 are} connected together to form a monocyclic hydrocarbon ring structure, and R ⁴ and R ^{5 are} connected Together to form a monocyclic hydrocarbon ring structure, and R ⁷ and R ⁸ may be H or methyl.

In some embodiments, the BODIPY portion of the present invention may include the following BODIPY portion, wherein R ¹ and R ⁶ may be alkenyl groups, R ² and R ^{3 are} connected together to form a polycyclic hydrocarbon ring structure, and R ⁴ and R ^{5 are} connected Together to form a polycyclic hydrocarbon ring structure, and R ⁷ and R ⁸ may be H or methyl.

。In some embodiments, R ² and R ⁵ may be substituted esters, where the substituted ester is an aryl ester. The aryl ester may have the following structure:

.

。In some embodiments, R ² and R ⁵ may be substituted esters, where the substituted ester is an alkyl ester. The alkyl ester may have the following structure:

.

。In some embodiments, R ¹ and R ⁶ may be substituted alkenyl groups. The substituted alkenyl group may 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 connected together to form another monocyclic hydrocarbon ring structure or a polycyclic hydrocarbon ring structure. In an embodiment, in the case where R ¹ and R ^{2 are} connected together to form a monocyclic hydrocarbon ring structure, the structure may be selected from the following:

[Cyclobutane],

[Cyclopentane],

[Cyclohexane],

[Cycloheptane],

[Cyclooctane],

[Cyclohexene],

[Cyclohexa-1,4-diene],

[Cyclopentene],

[Cyclohexa-1,3 diene], or

[Cyclododecane]. In some embodiments, where R ² and R ^{3 are} connected together to form a polycyclic hydrocarbon ring structure, the structure may be selected from the following:

[Dicyclooctane],

[Dicyclopentane],

[Dicycloheptane],

{Bicyclo[4.1.0]heptane],

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

[Decahydronaphthalene],

[Octahydrocyclopentadiene],

[Octahydroindene],

[Hexahydroindene],

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

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

[1,1-Dimethyl-2,3-dihydro-1 H -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, R ⁴ and R ⁵ may be connected together to form another monocyclic hydrocarbon ring structure or a polycyclic hydrocarbon ring structure. In an embodiment, in the case where R ⁵ and R ^{6 are} connected together to form a monocyclic hydrocarbon ring structure, the structure may be selected from the following:

[Cyclobutane],

[Cyclopentane],

[Cyclohexane],

[Cycloheptane],

[Cyclooctane],

[Cyclohexene],

[Cyclohexa-1,4-diene],

[Cyclopentene],

[Cyclohexa-1,3 diene], or

[Cyclododecane]. In some embodiments, where R ⁴ and R ^{5 are} connected together to form a polycyclic hydrocarbon ring structure, the structure may be selected from the following:

[Dicyclooctane],

[Dicyclopentane],

[Dicycloheptane],

[Bicyclo[4.1.0]heptane],

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

[Decahydronaphthalene],

[Octahydrocyclopentadiene],

[Octahydroindene],

[Hexahydroindene],

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

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

[1,1-Dimethyl-2,3-dihydro-1 H -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 composite may include a BODIPY moiety having the following chemical formula:

; Wherein R ¹ and R ² can be connected together to form another monocyclic hydrocarbon ring structure or polycyclic hydrocarbon ring structure; R ³ and R ⁴ can be H; R ⁵ and R ⁶ can be connected together to form another single Cyclic hydrocarbon ring structure or polycyclic hydrocarbon ring structure; R ⁷ and R ^{8 are} independently selected from H, methyl, or ether groups; and L represents a linking group including a substituted ester linking group .

In some embodiments, R ¹ and R ² can be connected together to form a polycyclic hydrocarbon ring structure; R ³ and R ⁴ are both methyl groups; R ⁵ and R ⁶ can be connected 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 may be connected together to form another monocyclic hydrocarbon ring structure or a polycyclic hydrocarbon ring structure. In an embodiment, in the case where R ¹ and R ^{2 are} connected together to form a monocyclic hydrocarbon ring structure, the structure may be selected from the following:

[Cyclobutane],

[Cyclopentane],

[Cyclohexane],

[Cycloheptane],

[Cyclooctane],

[Cyclohexene],

[Cyclohexa-1,4-diene],

[Cyclopentene],

[Cyclohexa-1,3 diene], or

[Cyclododecane]. In some embodiments, where R ¹ and R ^{2 are} connected together to form a polycyclic hydrocarbon ring structure, the structure may be selected from the following:

[Dicyclooctane],

[Dicyclopentane],

[Dicycloheptane],

{Bicyclo[4.1.0]heptane],

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

[Decahydronaphthalene],

[Octahydrocyclopentadiene],

[Octahydroindene],

[Hexahydroindene],

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

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

[1,1-Dimethyl-2,3-dihydro-1 H -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 connected together to form another monocyclic hydrocarbon ring structure or a polycyclic hydrocarbon ring structure. In an embodiment, in the case where R ⁵ and R ^{6 are} connected together to form a monocyclic hydrocarbon ring structure, the structure may be selected from the following:

[Cyclobutane],

[Cyclopentane],

[Cyclohexane],

[Cycloheptane],

[Cyclooctane],

[Cyclohexene],

[Cyclohexa-1,4-diene],

[Cyclopentene],

[Cyclohexa-1,3 diene], or

[Cyclododecane]. In some embodiments, where R ⁵ and R ^{6 are} connected together to form a polycyclic hydrocarbon ring structure, the structure may be selected from the following:

[Dicyclooctane],

[Dicyclopentane],

[Dicycloheptane],

{Bicyclo[4.1.0]heptane],

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

[Decahydronaphthalene],

[Octahydrocyclopentadiene],

[Octahydroindene],

[Hexahydroindene],

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

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

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

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

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

In some embodiments, the distance between the blue light-absorbing azole derivative and the BODIPY portion may be about 8Å or greater. The linking group can maintain the distance between the blue light-absorbing azole derivative and the BODIPY moiety.

In some embodiments, the photoluminescent composite includes a linker group, wherein the linker group covalently connects the blue light-absorbing azole derivative to the BODIPY moiety. In some embodiments, the linking group may comprise a single bond between the azole derivative and the BODIPY moiety.

。In some embodiments, the linker group may include an optionally substituted C ₂ -C ₁₆ ester group. When the linking group includes a substituted ester group, the linking group can be:

.

。In some embodiments, the linker group may include an unsubstituted ester group. When the linking group includes an unsubstituted ester group, the linking group can be:

.

。The photoluminescent composite of the present invention can be represented by the following structures, which are provided for illustrative purposes and must not be construed as restrictive:

.

In some embodiments, the photoluminescent composite includes a blue light-absorbing azole derivative. The blue light-absorbing azole derivative may include an organic luminescent group. In some embodiments, the azole derivative can be used in the range of 400 nm to about 480 nm, about 400 nm to about 410 nm, about 410 nm to about 420 nm, about 420 nm to about 430 nm, and about 430 nm to about 430 nm. 440 nm, about 440 nm to about 450 nm, about 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 Any wavelength of light has the maximum absorbance. In some embodiments, the maximum absorbance peak of the photoluminescent composite may be about 450 nm. In other embodiments, the blue light-absorbing azole derivative may have a maximum peak absorbance of about 405 nm. In other embodiments, the blue light-absorbing azole derivative may have a maximum peak absorbance of about 480 nm.

Some embodiments include a color conversion film including: a color conversion layer, the color conversion layer including a resin matrix; and the aforementioned photoluminescent composite, the photoluminescent composite dispersed in the resin matrix. In some embodiments, the color conversion film can be described as a combination comprising the composite described herein.

Some embodiments include a color conversion film that may have a thickness of about 1 μm to about 200 μm. 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 8-9 µm, about 9-10 µm, about 1-5 µm, about 5-10 µm, about 10-15 µm, about 15-20 µm, about 20-40 µm, about 40-80 µm, about 80-120 µm, about 120-160 µm, about 160-200 µm, or any thickness within the range defined by any of these equivalent values.

In some embodiments, the color conversion film can absorb light in a wavelength range of 400 nm to about 480 nm, and can emit light in a range of about 510 nm to about 560 nm or about 610 nm to about 645 nm. In other embodiments, the color conversion 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 opposite surfaces, wherein the color conversion layer can be disposed on the surface of the transparent layer that will be adjacent to the light source and physically contact the surfaces. There is no particular limitation on the transparent substrate, and those familiar with the art will be able to select a transparent substrate from among the transparent substrates 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) Glycol formate), PDMS (polydimethylsiloxane), COC (cycloolefin copolymer), PGA (polyglycolide or polyglycolic acid), PLA (polylactic acid), PCL (polycaprolactone) ), PEA (polyethylene adipate), PHA (polyhydroxy fatty acid ester), PHBV (poly(3-hydroxybutyrate-co-poly-3-hydroxyvalerate)), PBE (poly(terephenylene) Butylene dicarboxylate), PTT (polytrimethylene terephthalate), etc.

In some embodiments, the transparent substrate may have two opposite surfaces. In some embodiments, the color conversion film may be disposed on one of the opposing surfaces and in physical contact with the surface. 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 preparation 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 can be used as a support. Those familiar with this technology can determine which material and thickness to use as the supporting substrate.

Some embodiments include a method for preparing a color conversion film, wherein the method includes: dissolving the photoluminescent compound and the binder resin described herein in a solvent; and applying the mixture to the 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 resin, vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral resin, polyvinyl phosphonic acid (PVPA), polystyrene resin, phenolic resin, phenoxy resin, polyvinyl, nylon, fiber Plain resin and cellulose acetate resin. In some embodiments, the adhesive resin may be polyester resin and/or acrylic resin.

Solvents that can be used to dissolve or disperse compounds 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, undecyl alcohol, diacetone alcohol and furfuryl alcohol; Cellosolves™, such as methyl Cellosolve™, ethyl Cellosolve ™, butyl Cellosolve™, methyl Cellosolve™ acetate and ethyl Cellosolve™ 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 diethylene and tetrahydrofuran ; Ester, such as butyl acetate, pentyl acetate, ethyl butyrate, butyl butyrate, diethyl oxalate, ethyl pyruvate, ethyl 2-hydroxybutyrate, ethyl acetate, methyl lactate, 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 may include the above-mentioned color conversion film.

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

Unless otherwise specified, all numbers used in the specification and examples representing the amounts of ingredients, properties (such as molecular weight), reaction conditions, etc., should be understood as being modified by the term "about" in all cases. Therefore, unless there is an instruction to the contrary, the numerical parameters listed in the specification and the appended embodiments are approximate values, and these approximate values may vary according to the desired properties sought to be obtained. In any case, it is not an attempt to limit the application of the principle of equivalents. For the scope of the embodiment, each numerical parameter should be explained at least based on the number of significant digits reported and by applying common rounding techniques.

For the disclosed processes and/or methods, the functions performed in the processes and methods can be implemented in a different order, as the context dictates. In addition, the outlined steps and operations are only provided as examples, and some of the steps and operations can be selected as appropriate, combined into fewer steps and operations, or expanded into additional steps and operations.

The present invention may sometimes describe different components included in or connected to different other components. The architecture depicted in this way is only an example, and can be many other architectures that achieve the same or similar functionality.

The terms used in the present invention and the accompanying embodiments (for example, the main body of the appended embodiments) are generally intended as "open" terms (for example, the term "including" should be interpreted as "including but not limited to", and the term "having" Should be interpreted as "at least with", the term "including" should be interpreted as "including but not limited to" etc.). In addition, if a specific quantity of elements is introduced, this can be interpreted as at least the stated quantity, as can be dictated by the context (for example, the expression "two descriptive items" without other modifiers means two or At least two of the more narrative items). As used in the present invention, transitional words and/or phrases that present two or more alternatives should be understood to include one of these items, any or all of these items The possibility of these 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 specified herein or clearly contradictory to the context, the terms "a/an" and "the/the (the) are used in the context of describing the present invention (especially in the context of the following embodiments). "And similar denominations should be interpreted as covering both the singular and the plural. The use of any and all examples or representative language (such as "for example") provided herein is only intended to better illustrate the present invention, and does not limit the scope of any embodiment. Any language in the specification should not be construed as indicating any unrepresented element that is indispensable for the implementation of the present invention.

The grouping of alternative elements or embodiments disclosed herein should not be construed as limiting. Each group member can be mentioned and embodied individually or in any combination with other members of the group or other elements found in this document. It is expected that one or more members of the group may be included in the group or deleted from the group for reasons of convenience and/or patentability. When any such inclusion or deletion occurs, this specification is deemed to include the modified group so as to satisfy the written description of all Markush groups used in the appended embodiments.

Certain embodiments are described herein, including the best mode known to the inventors for carrying out the invention. Of course, for those who are generally familiar with the technology, after reading the foregoing description, the variations of the described embodiments will become obvious. The present inventor hopes that the skilled person appropriately adopts such modifications, and the present inventor hopes to practice the present invention in a manner different from that specifically described herein. Therefore, the embodiments include all modifications and equivalents of the subject matter described in the embodiments permitted by applicable laws. In addition, unless otherwise stated herein or clearly contradicting the context, any combination of all possible variations of the aforementioned elements is contemplated. Finally, it should be understood that the embodiments disclosed herein are descriptions of the principles of the embodiments. Other modifications that can be adopted are within the scope of the embodiment. Therefore, by way of example and not limitation, alternative embodiments may be utilized according to the teachings herein. Therefore, the embodiments are not limited to exactly as shown and described.

， 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。 連接基基團，其中該連接基基團為非取代之酯或經取代之酯；以及 二吡咯亞甲基硼(BODIPY)部分； 其中該連接基基團共價連接該唑類衍生物與該BODIPY部分，其中該唑類衍生物吸收第一激發波長之光能且將能量轉移至該BODIPY部分，其中該BODIPY部分吸收來自該唑類衍生物的該能量且發射第二更高波長之光能，且其中該光致發光複合物之發射量子產率大於80%。 EXAMPLES Example 1 A photoluminescent composite, the photoluminescent composite comprising: a blue-light absorbing azole derivative, and the blue-light absorbing azole derivative has the following general formula:

, Wherein Z is NR ¹⁰ , O or S; R ^{9 is} selected from H, unsubstituted ester linking group, or substituted ester linking group; and R ^{10 is} selected from H, substituted aryl, non- A substituted ester linker group, or a substituted ester linker group. A linking group, wherein the linking group is an unsubstituted or substituted ester; and a BODIPY moiety; wherein the linking group covalently connects the azole derivative and the BODIPY part, wherein the azole derivative absorbs light energy at a first excitation wavelength and transfers energy to the BODIPY part, wherein the BODIPY part absorbs the energy from the azole derivative and emits light energy at a second higher wavelength , And the emission quantum yield of the photoluminescence composite 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 linker, 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 linker, 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 part 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 R ^{5 are} independently selected from H, saturated alkyl, unsaturated alkyl, cyano (-CN), alkyl ester, or aryl ester; R ² and R ³ can be joined together to form another monocyclic hydrocarbon Ring structure or polycyclic hydrocarbon ring structure; R ⁴ and R ⁵ can be connected together to form another monocyclic hydrocarbon ring structure or polycyclic hydrocarbon ring structure; R ⁷ and R ⁸ can be independently selected from H and methyl groups ; And L represents a linking group, and the linking group includes a substituted ester linking 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 all cyano ^{groups, R 7} and R ⁸ are all methyl groups, and L It is a 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, R ⁷ and R ⁸ are all methyl groups, And L is a linking group.

Example 10 is the BODIPY part of Example 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.

Example 11 is the BODIPY portion of Example 7, wherein R ¹ and R ⁶ are each an alkenyl group, R ² and R ^{3 are} connected together to form a monocyclic hydrocarbon ring structure, and R ⁴ and R ^{5 are} connected together to form In a 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 portion 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 photoluminescence composite of embodiment 1, wherein the BODIPY part has the following general formula:

, R ¹ and R ^{2 are} connected together to form another polycyclic hydrocarbon ring structure; R ³ and R ⁴ are both methyl groups; R ⁵ and R ^{6 are} connected together to form another polycyclic hydrocarbon ring structure; R ⁷ and R ⁸ may be independently selected from H, methyl, or ester groups; and L represents a linking group, and the linking group includes a substituted ester linking group.

Embodiment 14 is the BODIPY part of embodiment 13, wherein R ¹ and R ^{2 are} connected together to form a polycyclic hydrocarbon ring structure, R ³ and R ⁴ are both methyl groups, and R ⁵ and R ⁶ can be connected together to form a polycyclic hydrocarbon ring structure. In the 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 composite of Embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, and 14, wherein the unsubstituted ester linking group is the following:

.

。 Embodiment 16 is the photoluminescent composite 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:

.

。 Embodiment 17 is the photoluminescent composite of embodiment 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, and 14, wherein the photoluminescent composite is selected from the following 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 includes a resin matrix, and at least one photoluminescence compound, wherein the at least one photoluminescence compound comprises such as The photoluminescent compounds of Examples 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 and 13, the photoluminescent compounds are dispersed in the resin matrix.

Embodiment 19 is the color conversion film of Embodiment 18, and the color conversion film also contains a singlet oxygen quencher.

Example 20 is the color conversion film of Example 18, and the color conversion film also contains 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 conversion 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 for preparing the color conversion film as in Embodiments 18, 19, 20, and 21, the method includes: The photoluminescent composites of 11, 12, 13, 14, 15, 16, and 17 and the binder resin are dissolved in a solvent; and the mixture is applied to one of the opposite surfaces of the transparent substrate.

Embodiment 24 is a backlight unit that includes the color conversion film of Embodiments 18, 19, 20, and 21.

Embodiment 25 is a display device including the backlight unit as in embodiment 24.

Examples It has been found that the embodiments of the photoluminescent composite described herein have improved performance compared to other forms of dyes used in color conversion films. These benefits are further demonstrated by the following examples, which are only intended to illustrate the present invention, and not intended to limit the scope or basic principles in any way.

CE-1 ： 將0.75 g的4-羥基-2,6-二甲基苯甲醛(5 mmol)及1.04 g的2,4-二甲基吡咯(11 mmol)溶於100 mL的無水二氯甲烷中。將溶液脫氣30分鐘。然後加入一滴三氟乙酸。將溶液在氬氣氛圍下在室溫下攪拌隔夜。向所得溶液中加入DDQ (2.0 g)，且將混合物攪拌隔夜。第二天將溶液過濾，然後用二氯甲烷洗滌，得到二吡咯甲烷(1.9 g)。接下來，將1.0 g的二吡咯甲烷溶於60 mL的THF中。將5 mL的三甲胺添加至該溶液中，然後脫氣10分鐘。在脫氣後，緩慢加入5 mL三氟硼-二乙醚，然後在70℃加熱30分鐘。將所得溶液加載至矽膠上，且藉由使用二氯甲烷作為溶離劑的快速層析法純化。收集所需級分，且減壓乾燥，得到0.9 g的橙色固體(76%產率)。LCMS (APCI+)：C₂₁ H₂₄ BF₂ N₂ O (M+H)之計算值=369；實測值：369。¹ H NMR (400 MHz，氯仿-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 1.1 Comparative Example 1 (CE-1) :

CE-1 : Dissolve 0.75 g of 4-hydroxy-2,6-dimethylbenzaldehyde (5 mmol) and 1.04 g of 2,4-dimethylpyrrole (11 mmol) in 100 mL of anhydrous dichloromethane middle. The solution was degassed for 30 minutes. Then add one drop of trifluoroacetic acid. The solution was stirred overnight at room temperature 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 then washed with dichloromethane to obtain dipyrromethene (1.9 g). Next, 1.0 g of dipyrromethene was dissolved in 60 mL of THF. Add 5 mL of trimethylamine to the solution and degas for 10 minutes. After degassing, 5 mL of trifluoroboron-diethyl ether was slowly added, and then heated at 70°C for 30 minutes. The resulting solution was loaded on silica gel and purified by flash chromatography using dichloromethane as the eluent. The desired fractions were collected and dried under reduced pressure to obtain 0.9 g of an orange solid (76% yield). LCMS (APCI+): _{Calculated value of C 21} H ₂₄ BF ₂ N ₂ O (M+H)=369; actually measured value: 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.

化合物 1.1 (4-(4-((4-(7-(4-( 二苯基胺基 ) 苯基 ) 苯并 [c][1,2,5] 噻二唑 -4- 基 ) 苯基 )( 苯基 ) 胺基 ) 苯基 )-4- 側氧基丁酸 ) ：

步驟 1 ：化合物 1.1.1(4-(4-((4-(7-(4-( 二苯基胺基 ) 苯基 ) 苯并 [c][1,2,5] 噻二唑 -4- 基 ) 苯基 )( 苯基 ) 胺基 ) 苯基 )-4- 側氧基丁酸甲酯 ): 在300 mL的3頸圓底燒瓶中裝入攪拌棒，且用氬氣吹掃。在室溫在攪拌下向該燒瓶中加入4,4'-(苯并[c][1,2,5]噻二唑-4,7-二基)雙(N,N-二苯基苯胺)(根據US 9,399,730B2製備，1.00 mmol，623 mg)、無水DCM (20 mL)，之後加入ZnCl₂ (1.0 M的Et₂ O溶液，6.0 mmol，6.00 mL)。藉由注射器向該經攪拌之混合物中加入4-氯-4-側氧基丁酸甲酯(5.0 mmol，0.616 mL)。將反應混合物在室溫下攪拌24小時，然後在氬氣下加熱至50℃達2天。將反應混合物冷卻至室溫，且用DCM (250 mL)及水(100 mL)分配。將各層分離，將水層用DCM (2×20 mL)萃取，將合併之有機層用鹽水(20 mL)洗滌，經MgSO₄ 乾燥，過濾且真空濃縮。藉由使用乙酸乙酯/DCM梯度(100% DCM (1 CV)à10% EtOAc/DCM (10 CV))在矽膠上進行快速層析法來純化。得到248 mg的化合物1.1.1(產率34%)。MS (APCI)：C₄₇ H₃₆ N₄ O₃ S (M-H)之計算值=735；實測值=7735。¹ H NMR (400 MHz，氯仿-d ) δ 7.95 (d,J = 8.2 Hz, 2H), 7.88 (t,J = 7.8 Hz, 4H), 7.77 (s, 2H), 7.37 (t,J = 7.7 Hz, 2H), 7.33-7.22 (m, 6H), 7.24-7.15 (m, 8H), 7.12 (d,J = 8.5 Hz, 2H), 7.07 (t,J = 7.4 Hz, 2H), 3.71 (s, 3H), 3.27 (t,J = 6.7 Hz, 2H), 2.76 (t,J = 6.7 Hz, 2H)。 Example 2 : Synthesis of photoluminescent composite: 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 -oxobutyric 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-oxo butanoate side): stir bar was charged in a 300 mL 3-neck round bottom flask, and purged with argon. Add 4,4'-(benzo[c][1,2,5]thiadiazole-4,7-diyl)bis(N,N-diphenylaniline) to the flask under stirring at room temperature ) (Prepared according to US 9,399,730B2, 1.00 mmol, 623 mg), anhydrous DCM (20 mL), and then add ZnCl ₂ (1.0 M in Et ₂ O solution, 6.0 mmol, 6.00 mL). To the stirred mixture was added methyl 4-chloro-4-oxobutanoate (5.0 mmol, 0.616 mL) via a syringe. The reaction mixture was stirred at room temperature for 24 hours and then heated to 50°C for 2 days under argon. 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 (2×20 mL), the combined organic layer was washed with brine (20 mL), dried over MgSO ₄ , filtered and concentrated in vacuo. Purification was performed by flash chromatography on silica gel using an ethyl acetate/DCM gradient (100% DCM (1 CV)→10% EtOAc/DCM (10 CV)). Obtained 248 mg of compound 1.1.1 (yield 34%). MS (APCI): _{calculated value of C 47} H ₃₆ N ₄ O ₃ S (MH)=735; measured value=7735. ¹ H NMR (400 MHz, chloroform- d ) δ 7.95 (d, J = 8.2 Hz, 2H), 7.88 (t, J = 7.8 Hz, 4H), 7.77 (s, 2H), 7.37 (t, J = 7.7 Hz, 2H), 7.33-7.22 (m, 6H), 7.24-7.15 (m, 8H), 7.12 (d, J = 8.5 Hz, 2H), 7.07 (t, J = 7.4 Hz, 2H), 3.71 (s , 3H), 3.27 (t, J = 6.7 Hz, 2H), 2.76 (t, J = 6.7 Hz, 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 -oxobutanoic acid ) : A 250 mL 3-neck round bottom flask was charged with a stir bar and flushed with argon. KOH (3.26 mmol, 183 mg) was added to compound 1.1.1, followed by water (5 mL). The flask was equipped 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). Fill a 1 L Erlenmeyer flask 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 HCl aqueous solution to a pH of 3.5-4 (pH test 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 separated by filtration and dried in vacuum to obtain a quantitative yield. MS (APCI): _{The calculated value of C 46} H ₃₄ N ₄ O ₃ S (MH) = 721; the measured value = 721. The product has 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] diazepin-bora-benzo [4,3-a: 6,1-a '] di-indol-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 )) : Put a stirring rod in a 500 mL round bottom flask and flush with argon. 4,5,6,7-tetrahydro-2H -isoindole-1-carboxylic acid ethyl ester (10.0 mmol, 1.933 g) and 4-bromobenzaldehyde (6.00 mmol, 1110 mg) were added to the flask. Anhydrous dichloromethane (200 mL) was added, followed by p-TsOH (0.1 g). The flask was sealed and stirred at room temperature overnight under argon. The reaction mixture was evaporated to dryness and the residue was saponified without further purification. MS (APCI): _{calculated value of C 29} H ₃₃ BrN ₂ O ₄ (MH)=551; measured value: 551.

Compound 1.2.2 (14-(4- bromophenyl ) -7,7-difluoro- 5,9 -diiodo- 1,3,4,7,10,11,12,13- octahydro -2H- 6l4,7l4- [1,3,2] diazepin-bora-benzo [4,3-a: 6,1-a '] indol-diisopropyl): stir bar was charged in a 1 L round bottom flask. NaOH (6.00 g) and water (30 mL) were added to the flask. The mixture was stirred to obtain a solution, and the flask was flushed with argon gas. Compound 1.2.1 (assuming 5.0 mmol) was added to the reaction flask, followed by ethanol (200 proof, 300 mL). The flask was equipped 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 HCl aqueous solution. The mixture was diluted with water to a total volume of 1 L, and the precipitate was collected by suction filtration. The damp precipitate was placed in a 3 L 2-neck round bottom flask, and a stir bar was placed in the flask. The flask was flushed with argon. A solution of sodium bicarbonate (188.2 mmol, 15.81 g) was prepared in water (300 mL), and the solution was added to the reaction flask. Methanol (900 mL) was added with stirring to obtain a solution. Under an argon atmosphere, iodine (58.8 mmol, 14.92 g) was added to the flask under vigorous stirring. The reaction mixture was stirred at room temperature overnight. The precipitated intermediate was filtered off and washed with water. The product was vacuumed and then dried in a vacuum oven at 50°C. The dried precipitate was dissolved in anhydrous dichloromethane (500 mL) in a 1 L 2-neck round bottom flask flushed with argon equipped with a stir bar. The flask was sealed with a septum and cooled to -10°C (water-ice/methanol bath) under an argon atmosphere. _{Under vigorous stirring, BF 3} ·OEt ₂ (571.2 mmol, 70.5 mL) was added to the flask via a syringe. The flask was equipped with a dropping funnel, and anhydrous triethylamine (331.5 mmol, 46.2 mL) was placed in the dropping funnel. Triethylamine was added dropwise within 5 minutes under 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 adding 1N aqueous HCl (200 mL). The layers were separated, and the organic layer was washed sequentially with 1N aqueous HCl (200 mL), saturated aqueous sodium bicarbonate (3×200 mL), and brine (200 mL). The organic layer was dried over MgSO _4, filtered, and concentrated by rotary evaporation. Methanol was added to the crude purple-black liquid. 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 obtain 1.888 g of the desired product (yield 64%). MS (APCI): _{Calculated value of C 23} H ₂₀ BBrF ₂ I ₂ N ₂ (MH)=705; actually measured value: 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] diazepin-bora-benzo [4,3-a: 6,1-a '] indol-5,9-diisopropyl-yl) (2E, 2'E) - diethyl diacrylate): a solution of 250 mL 2 neck round bottom flask fitted with a reflux condenser and charged with the rod, and flushed with argon. 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) were added to the flask. Add inhibitor-free THF (20 mL) and toluene (20 mL), and then add 1.0 MK ₂ CO ₃ aqueous solution (5.05 mmol, 5.05 mL). The oxygen in the flask was purged three times by vacuum/backfill with argon. 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 K ₂ CO ₃ aqueous solution (5.05 mL) was added, and the reaction was heated at 70° C. for another 2 hours. The reaction mixture was cooled to room temperature and partitioned with ethyl acetate (150 mL). The mixture was washed with saturated aqueous sodium bicarbonate solution (3×25 mL) and brine (25 mL). The reaction mixture was dried over MgSO ₄ , 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 product-containing fractions were concentrated in vacuo and triturated with methanol to remove co-dissolved impurities. 178 mg of compound 1.2.3 was obtained (yield 55%). MS (APCI): _{Calculated value of C 33} H ₃₄ BBrF ₂ N ₂ O ₄ (MH)=649; actually measured value: 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] diazepin-bora-benzo [4,3-a: 6,1-a '] di-indol-5, 9 -diyl ) (2E, 2'E)-diethyl diacrylate ) : A 250 mL 2-neck round bottom flask was filled with a stir bar and equipped with a reflux condenser, and flushed with argon. 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) were added to the flask. Add inhibitor-free THF (20 mL) and toluene (20 mL), and then add 1.0 MK ₂ CO ₃ aqueous solution (5.05 mmol, 5.05 mL). The oxygen in the flask was purged three times by vacuum/backfill with argon. 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 K ₂ CO ₃ aqueous solution (5.05 mL) was added, and the reaction was heated at 70° C. for another 2 hours. The reaction mixture was cooled to room temperature and partitioned with ethyl acetate (150 mL). The mixture was washed with saturated aqueous sodium bicarbonate solution (3×25 mL) and brine (25 mL). The reaction mixture was dried over MgSO ₄ , 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 product-containing fractions were concentrated in vacuo and triturated with methanol to remove co-dissolved impurities. 158 mg of compound 1.2 was obtained (90% yield). MS (APCI): _{calculated value of C 39} H ₃₉ BF ₂ N ₂ O ₅ (MH)=663; actually measured value: 663. Calculated value of (MH)=983; measured value: 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 -oxobutyryl ) oxy )-3,5 -dimethyl- [1,1' - biphenyl] -4-yl) -7,7-difluoro-octahydro -1,3,4,7,10,11,12,13- -2H-6l4,7l4- [1,3,2] Diazabora benzo [4,3-a:6,1-a'] diisoindole - 5,9-diyl )(2E,2'E)-diethyl diacrylate ) : at 40 Fill the mL screw cap vial with compound 1.2 (0.060 mmol, 42 mg), 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. Anhydrous THF (6 mL) was added to the vial, 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 MgSO _4, 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 obtain 54 mg of PLC-1 (65% yield). MS (APCI): _{calculated value of C 73} H ₇₅ BF ₂ N ₂ O ₆ (MH)=1395; measured value: 1395.

化合物 2.1.1 5-(4,7- 雙 (4-( 二苯基胺基 ) 苯基 )-2H- 苯并 [d][1,2,3] 三唑 -2- 基 ) 戊酸甲酯

Example 2.2 : PLC-2:

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

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

Step 2 : 5-(4,7 -Dibromo -2H- benzo [d][1,2,3] triazol -2- yl ) methyl valerate: Mix 2 g (7.2mmol, 1 equivalent) 4,7-dibromo-2H-benzo[d][1,2,3]triazole, 15.5 mL (21 mmol, 15 equivalents) methyl 5-bromopentanoate. Add 20 mL of N,N'-dimethylformamide. Then 5 g (36 mmol, 5 equivalents) of potassium carbonate was 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 the eluent. The desired product (1.8 g, yield 64%) was obtained as a clear viscous liquid. ¹ H NMR (400 MHz, 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 : 5-(4,7 -bis (4-( diphenylamino ) phenyl )-2H- benzo [d][1,2,3] triazol -2- yl ) valerate methyl ester ： Mix 1.8 g (4.6 mmol, 1 equivalent) 5-(4,7-dibromo-2H-benzo[d][1,2,3]triazol-2-yl)valerate methyl ester in a small flask , 10 mL n-butanol, 3 mL toluene and 3 mL deionized water. The solution was bubbled with argon for about 30 minutes. Subsequently, 3.99 g (13.81 mmol, 3 equivalents) (4-(diphenylamino)phenyl)boronic acid was added, followed by 6 g (56.61 mmol, 12.30 equivalents) potassium carbonate. Then 1.06 g (0.920 mmol, 0.2 equivalent) of palladium(triphenylphosphine)(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 the eluent. The desired product was obtained as a yellow powder, namely compound 2.1.1 (300 mg, yield 10%). ¹ H NMR (400 MHz, 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 Methyl-2-yl)valerate (compound 2.1.1, 0.425 mmol, 306 mg), and the flask was suspended in absolute ethanol (80 mL). The flask was equipped with a fin 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 under argon for 6 hours. 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 with 6N HCl to a pH of about 1. After acidification, the crude acid was separated by precipitation from water to obtain 289 mg of compound 2.1 (96% yield). The acid was used in the next step without further purification. MS (APCI): _{the calculated value of the chemical formula C 47} H ₃₉ N ₅ O ₂ (M-)=705; the measured value: 705.

Compound 2.2 :

Compound 2.2.1 (4,5 -dihydro- 1H- benzo [g] indole ) : Put a mixture of DMSO (50 mL), KOH (3.36 g) and NH ₂ OH·HCl (4.17 g) at room temperature After stirring for 30 minutes, a solution of 1-tetralone (7.3 g) in DMSO (25 ml) was added. The mixture was stirred at 70°C for another 30 minutes. Then KOH (8.41 g) was 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 NH ₄ Cl solution, and the solution was extracted with ethyl acetate (200 mL×3). The organic phase was collected and _{dried over Na 2} SO ₄ , concentrated to 10 mL, and then diluted with 10 mL dichloromethane and 50 mL hexane. The solution was subjected to flash chromatography (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 (3.5 g, yield 41%) was obtained. LCMS (APCI+): _{calculated value for C 12} H ₁₂ N (M+H): 170; found value: 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), 4-hydroxy-2,5-dimethylbenzaldehyde (0.15 g, 1 mmol) and a drop of trifluoroacetic acid in a mixture of 1,2-dichloroethane (20 mL) Air for 10 minutes, and then stir at 30°C for 20 hours. After cooling to room temperature, the mixture was filtered, and the solid was collected as compound 2.2.2 (0.2 g, yield 43%). LCMS (APCI+): _{calculated value for C 33} H ₃₁ N ₂ O (M+H): 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) using ice-water bath cooling at 0°C. The mixture was stirred for 20 minutes. Then 0.5 mL of trimethylamine was added to the resulting mixture, followed by 0.8 mL of BF ₃ -etherate. The whole was stirred overnight at room temperature, then loaded on silica gel, and purified by flash chromatography using dichloromethane/hexane (0%→80%) eluent. Collect the required red luminous fraction. After removing the solvent, a metallic dark red solid compound 2.2.2 was obtained (150 mg, 72% yield). LCMS (APCI+): _{calculated value of C 33} H ₂₈ BF ₂ N ₂ O (M+H): 517; found value: 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- k N ] difluoroboron ) : In a 40 mL screw cap vial, 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 anhydrous dichloromethane (20 mL) was added. Diisopropylcarbodiimide (0.300 mmol, 47 uL) was added, and the reaction was stirred at room temperature under argon overnight. The next morning, anhydrous tetrahydrofuran (10 mL) was added and sonicated for 30 seconds. Another portion of compound 2.1 was added and stirred at 50°C overnight under argon. Purify the crude by flash chromatography on silica gel (100% hexane (1 CV) → 50% DCM/hexane (0 CV) → 100% DCM (6 CV) → 10% EtOAc/DCM (10 CV)) product. The product-containing fractions were collected and evaporated to dryness to obtain 43 mg of PLC-2 (65% yield). MS (APCI): _{the calculated value of the chemical formula C 80} H ₆₄ BF ₂ N ₇ O ₂ (M-)=1203; the measured value: 1203. ¹ H NMR (400 MHz, chloroform-d) δ 8.80 (d, J = 8.0 Hz, 2H), 8.01 (d, J = 8.8 Hz, 4H), 7.61 (s, 2H), 7.45 (t, J = 7.7 Hz, 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 = 7.0 Hz, 2H), 2.90 (t, J = 7.2 Hz, 4H), 2.68 (t, J = 7.3 Hz, 2H), 2.63 (t, J = 7.0 Hz, 4H), 2.34 (p, J = 7.9, 7.3 Hz, 2H), 2.18 (s, 3H), 1.90 (p, J = 7.7, 7.1 Hz, 2H).

Example 2.3 : PLC-3

Compound 3.1 (4-(6',6' -difluoro -6'H- 5'l4,6'l4-dispirocyclo [ cyclopentane- 1,12'- indeno [2',1': 4 ,5] pyrrolo [1,2-c] indeno [2',1':4,5] pyrrolo [2,1-f][1,3,2] diazepine- 16',1''- cyclopentane ]-14' -yl )-3,5 -dimethylphenol: Step 1 : (1-(2- bromophenyl ) cyclopentan- 1- ol ): dried A 250 mL 2-neck round bottom flask was equipped with a gas adapter and a stir bar, and was flushed with argon. The flask was sealed with a septum, and magnesium chips (145 mmol, 3.525 g) and anhydrous THF (100 mL) were charged via a syringe. A dry 100 mL 2-neck round bottom flask was equipped with a gas adapter and flushed with argon. The flask was sealed with a septum and filled with anhydrous THF (60 mL). The 100 mL flask was charged with 1,5-dibromo Pentane (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 a syringe with vigorous stirring within 5 minutes. The ice-water bath was removed In addition, replace it with a room temperature water bath, and stir the reaction mixture at room temperature. When stirred at room temperature for 4 hours, the reaction became slightly turbid. A 1000 mL 2-neck round bottom flask was equipped with a gas adapter and a stirring rod, And flush with argon. The second 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 dual Grignard reagent solution was added via a cannula under 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 quenched with saturated ammonium chloride solution (50 mL). The reaction mixture was further diluted with water (500 mL) and extracted with ethyl acetate (3×150 mL). The combined organic The layer was washed with brine (150 mL), dried over MgSO ₄ , filtered, and evaporated to dryness to give a light yellow oil. This oil was pure enough to be used in the next step. 11.145 g (yield 92%). MS (APCI): _{calculated value of C 11} H ₁₃ BrO (M+H)=241; measured value: 241.

Step 2 : (3-(1-(2- Bromophenyl ) cyclopentyl )-1 -tosyl- 1H- pyrrole /2-(1-(2- bromophenyl ) cyclopentyl )-1 - toluene sulfonic acyl -1H- pyrrole): stir bar 250 mL 2 neck round bottom flask was charged, and a gas fitting adapter. The flask was flushed with argon, and 1-(2-bromophenyl)cyclopentan-1-ol (10.0 mmol, 2.412 g) was added to the flask. Anhydrous dichloromethane (100 mL) was added, and 1-tosyl-1H-pyrrole (11.0 mmol, 2.434 g) was added with stirring at room temperature. Aluminum chloride (11.5 mmol, 1.533 g) was added to the stirred mixture in one portion. The reaction was stirred overnight at room temperature under argon. The reaction was quenched with water (30 mL) under vigorous stirring. The layers were separated, and the aqueous layer was extracted with dichloromethane (3×25 mL). The combined organic layer was washed with brine (25 mL), dried over MgSO ₄ , filtered, and evaporated to dryness. The crude product was purified by flash chromatography (100% hexane (1 CV) à 15% EtOAc/hexane (10 CV)) on silica gel. The two possible isomers dissociated as a single peak on the silica gel, and also co-dissociated with the unreacted 1-toluenesulfonyl-1H-pyrrole, which was 1.311 g. It is ^{estimated that there is about 1.05 g of product by 1} H NMR, and the yield is 23%. The mixture was submitted to the next step without further purification. MS (APCI): _{calculated value of C 22} H ₂₂ BrNO ₂ S (M+H)=444; measured value: 444.

Step 3 : (2-(1-(2- Bromophenyl ) cyclopentyl )-1 -tosyl- 1H- pyrrole ) was placed in a 40 mL screw cap vial with a stir bar. To this vial was added the mixture from step 2 (estimated 2.37 mmol, 1.05 g). Flush the vial with argon. Potassium carbonate (4.86 mmol, 672 mg), Pd(PPh ₃ ) ₄ (0.0711 mmol, 82 mg) and anhydrous dimethylformamide (6 mL) were added to the vial. Purge the oxygen in the vial by vacuum/backfill argon cycle (3 times). The reaction mixture was stirred under argon in a heating block at 110°C overnight. The next morning, more potassium carbonate (4.86 mmol, 672 mg) and Pd(PPh ₃ ) ₄ (0.0711 mmol, 82 mg) were added, and heating was continued at 110° C. for another 24 hours. The reaction mixture was cooled to room temperature, diluted with water (100 mL), and extracted with ether (3×50 mL). The combined organic layer was washed with water (3×25 mL), brine (25 mL), dried over MgSO ₄ , filtered, and evaporated to dryness. The crude reaction mixture was purified by flash chromatography (10% DCM/hexane (1 CV) à 50% DCM/hexane (10 CV)) on silica gel. The desired product was co-dissociated with 1-toluene-1H-pyrrole, and ^{the yield estimated by 1} H NMR was 549 mg, and the yield was 64%. The mixture of the desired isomer and 1-tosyl-1H-pyrrole is sent to the next step without further purification. MS (APCI): _{Calculated value of C 22} H ₂₁ NO ₂ S (M+H)=364; measured value: 364.

Step 4 : (1'H- Spiro [ cyclopentane -1,4'- indeno [1,2-b] pyrrole ]) : Fill a 100 mL 2-neck round bottom flask with a stir bar and assemble Finned 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). KOH (18.0 mmol, 1.01 g) was added to the flask. Stopper the second neck and place the flask 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 into saturated ammonium chloride (25 mL) and water (100 mL). The product was filtered off, washed with water, dried, and purified by flash chromatography (100% hexane (1 CV)→20% EtOAc/hexane (10 CV)) on silica gel. The product-containing fraction was evaporated to dryness to obtain 279 mg (74% yield) without any contaminants. MS (APCI): _{Calculated value of C 15} H ₁₅ N (M+H)=210; measured value: 210. ¹ H NMR (400 MHz, chloroform-d) δ 8.24 (s, 1H), 7.33 (dt, J = 7.5, 1.0 Hz, 1H), 7.24-7.17 (m, 2H), 7.08 (td, J = 7.2, 1.7 Hz, 1H), 6.81 (t, J = 2.5 Hz, 1H), 6.19 (dd, J = 2.7, 1.8 Hz, 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-dispirocyclo [ cyclopentane- 1,12'- indeno [2',1': 4 ,5] pyrrolo [1,2-c] indeno [2',1':4,5] pyrrolo [2,1-f][1,3,2] diazepine- 16',1''- cyclopentane ]-14' -yl )-3,5 -dimethylphenol ) : A 250 mL 2-neck round bottom flask is equipped with a finned condenser, stir bar and gas adapter. Flush the flask with argon and add 1'H-spiro[cyclopentane-1,4'-indeno[1,2-b]pyrrole] (product from step 4 above) (1.31 mmol, 275 mg) And 4-hydroxy-2,6-dimethylbenzaldehyde (0.683 mmol, 103 mg), followed by anhydrous dichloroethane (50 mL). The solution was stirred and sparged with argon for 30 minutes, then trifluoroacetic acid (0.1% v/v, 50 uL) was added via a syringe, and argon bubbling was continued for another 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 to 0°C with an ice-water bath, 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 were added BF ₃ ·OEt ₂ (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 in 4 hours. The water bath was removed and replaced with a heating block, and the reaction was heated at 40°C 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. The precipitate was dried and purified by flash chromatography (100% DCM (4 CV)→5% EtOAc/DCM (5 CV)→5% EtOAc/DCM) on silica gel. The column is eluted until the tail product has been eluted. The product-containing fractions were evaporated to dryness, yielding 314 mg (85% yield). MS (APCI): _{The calculated value of C 39} H ₃₅ BF ₂ N ₂ O (M ^- )=596; the measured value is 596.

PLC-3 : (4-(4-((4-(7-(4-( diphenylamino ) phenyl ) benzo [c][1,2,5] thiadiazol- 4 -yl ) (Phenyl ) ( phenyl ) amino ) phenyl )-4- side oxybutyric acid 4-(6',6' -difluoro -6'H- 5'l4,6'l4-dispiro ( 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] diazepin boratabenzenes -16 ', 1''- cyclopentane] -14'--yl) -3,5-dimethylphenyl): compound 3.1 (0.100 mmol, 60 mg) and compound 1.1 (0.400 mmol, 289 mg) were synthesized in a manner similar to that of compound 2. The crude product was purified by flash chromatography on silica gel (30% DCM/hexane (1 CV)→50% DCM/hexane (8 CV)→100% DCM (8 CV)). The product-containing fractions were evaporated to dryness to obtain 84 mg of PLC-3 (65% yield). MS (APCI): _{The calculated value of the chemical formula C 85} H ₆₇ BF ₂ N ₆ O ₃ S (M-)=1300; the measured value: 1300.

PLC -4 ((T-4)-[2-[(4,5- 二氫 -2H- 苯并 [g] 吲哚 -2- 亞基 -kN)-(3,5- 二甲基 -4-(4-(4-((4-(7-(4-( 二苯基胺基 ) 苯基 ) 苯并 [c][1,2,5] 噻二唑 -4- 基 ) 苯基 )( 苯基 ) 胺基 ) 苯基 )-4- 側氧基丁酸酯 ) 苯基 ) 甲基 ]-4,5- 二氫 -1H- 苯并 [g] 吲哚 -kN] 二氟硼 ) ： 在40 mL螺旋蓋小瓶中裝入攪拌棒、化合物2.2 (0.100 mmol，60 mg)、化合物1.1 (0.150 mmol，51 mg)，以及DMAP:pTsOH 1:1鹽(0.200 mmol，59 mg)。用氬氣沖洗小瓶，且加入無水二氯甲烷(20 mL)。加入二異丙基碳二亞胺(0.300 mmol，47 uL)，且將反應在氬氣下在室溫下攪拌隔夜。第二天早晨，加入無水四氫呋喃(10 mL)且音波處理30秒。加入另一部分的化合物1.1 (0.150 mmol，51 mg)，且在氬氣下在50℃下攪拌隔夜。藉由在矽膠上的快速層析法(100% DCM (5 CV)à5% EtOAc/DCM (5 CV)，然後10% EtOAc/己烷(1 CV)à 20% EtOAc/己烷(0 CV)à50% EtOAc/己烷(10 CV)，且最終5% EtOAc/甲苯(1 CV)à15% EtOAc/甲苯(10 CV))來純化粗產物。將含有產物之級分蒸發至乾，得到40 mg的PLC-4 (產率為33%)。MS (APCI)：化學式C₇₉ H₅₉ BF₂ N₆ O₃ S (M-)之計算值=1220；實測值：1220。 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 ) : Fill a 40 mL screw cap vial 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 anhydrous dichloromethane (20 mL) was added. Diisopropylcarbodiimide (0.300 mmol, 47 uL) was added, and the reaction was stirred at room temperature under argon overnight. The next morning, anhydrous 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/hexane (1 CV)→20% EtOAc/hexane (0 CV) →50% EtOAc/hexane (10 CV), and finally 5% EtOAc/toluene (1 CV)→15% EtOAc/toluene (10 CV)) to purify the crude product. The product-containing fractions were evaporated to dryness to obtain 40 mg of PLC-4 (yield 33%). MS (APCI): _{The calculated value of the chemical formula C 79} H ₅₉ BF ₂ N ₆ O ₃ S (M-) = 1220; the measured value: 1220.

化合物 5.1 [5,5- 二氟 -10-(4- 羥基 -2,6- 二甲基苯基 )-1,3,7,9- 四甲基 -5H-4l4,5l4- 二吡咯并 [1,2-c:2',1'-f][1,3,2] 二氮雜硼雜苯 -2,8- 二羧酸二苄酯 ]：

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] diazepin boratabenzenes 2,8-dicarboxylic acid dibenzyl]:

In a 250 mL round bottom flask, 40 mL (241 mmol) of tert-butyl 3-oxobutyrate 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 insoluble matter was filtered off to obtain a crude oxime solution, which was used in the next step without further purification. Then, 50 g of zinc powder (0.76 mol) was added in batches to a mixture of 13.7 mL (79 mmol) of benzyl 3-oxobutyrate and 100 mL of acetic acid. The resulting mixture was stirred in an oil bath and heated to 60°C. Slowly add the crude solution of tert-butyl 2-(hydroxyamino)-3-oxobutyrate. Then the temperature was 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 obtain 2,4-dimethyl- 1H -pyrrole-3-carboxylic acid benzyl ester, which was recrystallized from MeOH as a white solid to obtain 15 g, based on 3-oxobutane The yield of benzyl acid is 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, 2CH ₃ ), 1.56 (s, 9H, 3CH ₃ ).

Next, in a 25 mL vial, a mixture of 1 g (4.36 mmol) of 2,4-dimethyl-1 H -pyrrole-3-carboxylic acid benzyl ester and 0.524 g (4.36 mmol) of MgSO ₄ was dissolved in In 8 mL of anhydrous DCE, and stirred at room temperature in the presence of argon for 15 minutes. 0.327 g of 2,6-dimethyl 4-hydroxybenzaldehyde (2.18 mmol) was added in multiple small portions; finally, it was closed with a Teflon cap. The resulting mixture was continuously purged with argon for 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 has been consumed. 0.544 g (2.398 mmol) of DDQ was added to the crude product in one portion. The resulting mixture was stirred at room temperature for ½ hour. TLC and LCMS showed that the starting material has been consumed. The resulting mixture was filtered through short-path celite; the filtrate was concentrated to dryness, the residue was redissolved in 50 mL of DCE, stirred with trimethylamine (1.4 mL, 19 mmol) at room temperature for 15 minutes, and then cooled To 0°C. Slowly add 3 mL of BF ₃ ·OEt ₂ (18.36 mmol). The resulting mixture was stirred at room temperature for ½ hour and then heated to 86°C for 45 minutes. The reaction mixture was then _{diluted with 150 mL of CHCl 3} and quenched with 50 mL of brine. The organic layer was separated, and dried with MgSO _4, and solvent was removed rotary evaporation. The residue was chromatographed on a silica gel column using CH ₂ Cl ₂ /EtOAc as the eluent to obtain 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]diazepine- Dibenzyl 2,8-dicarboxylic acid), namely compound 5.1, is an orange-red solid with a yield of 72% based on 2,6-dimethyl 4-hydroxybenzaldehyde. LCMS (APCI-), _{calculated value of M- for C 37} H ₃₅ BF ₂ N ₂ O ₅ : 636.26; actually measured value: 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 = 5.4 Hz, 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) pent-acyl) oxy) -2,6-dimethylphenyl) -1,3,7,9- tetramethyl-5,5-difluoro -5H-4l4,5l4- dipyrrole and [1,2-c: 2 ', 1'-f] [1,3,2] diazepin boratabenzenes 2,8-dicarboxylic acid dibenzyl ester): compound 2.1 (0.050 mmol, 32 mg) and compound 5.1 (0.060 mmol, 42 mg) were prepared in a manner similar to compound 2 to prepare PLC-5. Purify the crude product 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 product-containing fraction was evaporated to dryness to obtain 43 mg of PLC-5 (65% yield). MS (APCI): _{the calculated value of the chemical formula C 84} H ₇₂ BF ₂ N ₇ O ₆ (M-)=1323; the measured value: 1323. ¹ H NMR (400 MHz, chloroform-d) δ 8.00 (d, J = 8.7 Hz, 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 = 7.0 Hz, 2H), 2.82 (s, 6H), 2.65 (t, J = 7.3 Hz, 2H), 2.32 (p, J = 7.6, 7.1 Hz, 2H), 2.06 (s, 6H), 1.86 (p, J = 7.2 Hz, 2H), 1.67 (s, 6H).

化合物 6.1.1  4-(4-(4,7- 雙 (4-( 二苯基胺基 ) 苯基 )-2H- 苯并 [d][1,2,3] 三唑 -2- 基 ) 苯基 ) 丁酸甲酯

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 ) methyl butyrate

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

Step 2.4, 4'-(2H -benzo [d][1,2,3] triazole -4,7 -diyl ) bis (N,N -diphenylaniline ) : equipped with 2 g (7.2 mmol, 1 equivalent) of 4,7-dibromo-2H-benzo[d][1,2,3]triazole was added to the 2-neck flask of the condenser. Add 10 mL n-butanol, 3 mL toluene and 3 mL water. The mixture was heated to 45°C (while bubbling at the same time) for 30 minutes. Add 5.22 g (18 mmol, 2.50 equivalents) (4-(diphenylamino)phenyl)boronic acid, followed by 9.19 g (87 mmol, 12 equivalents) potassium carbonate. The temperature of the solution was increased to 110°C. Then 1.67 g (0.144 mmol, 0.2 equivalent) of palladium(triphenylphosphine)(0) was added. A total of 5 g additional boric acid, 2 g base, and 0.5 g catalyst are added. After about 4.5 hours, the reaction was cooled. The reaction was poured into 200 mL methanol. After stirring for a few minutes, the precipitate precipitated out. Column chromatography was performed using hexane: ethyl acetate (9:1). The desired product (1.74 g, yield 40%) was obtained as a bright orange powder.

Step 3 : 4-(4-(4,7 -bis (4-( diphenylamino ) phenyl )-2H- benzo [d][1,2,3] triazol -2- yl ) benzene yl) butanoate: under argon was added a solution of 2-necked flask equipped with a condenser, 150 mg (583 mmol, 1 eq.) of 4,4 'from the previous step - (2H- benzo [d] [1 ,2,3]triazole-4,7-diyl)bis(N,N-diphenylaniline). Subsequently, 2 mL of anhydrous toluene was added, followed by 248 mg (1.2 mmol, 2 equivalents) of potassium phosphate. In a separate vial under argon, add 44 mg (53 µmol, 0.1 equivalent) of ginseng (dibenzylideneacetone) dipalladium (0) and 55 mg (117 µmol, 0.2 equivalent) of di-tertiary butyl (2',4',6'-Triisopropyl-3,4,5,6-tetramethyl-[1,1'-biphenyl]-2-yl)phosphorane. Purge the vial with argon for 15 minutes. Then add 2 mL of anhydrous toluene. The flask was heated at 120°C for 3 minutes. Place the first flask in a heating block at 120°C. The contents of the vial containing the ligand and catalyst are 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 was obtained as an orange powder, namely compound 6.1.1 (120 mg, 26%). ¹ H NMR (400 MHz, 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 equipped with a fin 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 under argon for 6 hours. The reaction was cooled to room temperature, and the reaction mixture was evaporated to dryness. The crude precipitate was isolated in a quantitative yield to obtain compound 6.1, which was used in the next step without further purification. MS (APCI): _{The calculated value of the chemical formula C 52} H ₄₁ N ₅ O ₂ (MH)=765, the measured value: 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 - two-pyrrolo [1,2-c: 2 ', 1'-f] [1,3,2] diazepin boratabenzenes 2,8-dicarboxylic acid dibenzyl ester): in 40 mL screw-cap The vial was charged with a stir bar, 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 anhydrous dichloromethane (20 mL) was added. Diisopropylcarbodiimide (0.300 mmol, 47 µL) was added, and the reaction was stirred at room temperature under argon overnight. The next morning, anhydrous tetrahydrofuran (10 mL) was added and sonicated for 30 seconds. An additional portion of compound 6.1 was added and stirred at 50°C overnight 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)). The product-containing fractions were evaporated to dryness to obtain 57 mg of PLC-6 (83% yield). MS (APCI): _{The calculated value of the chemical formula C 89} H ₇₄ BF ₂ N ₇ O ₆ (M-)=1385; the measured value: 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 = 8.5 Hz, 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 = 7.5 Hz, 2H), 2.17-2.09 (m, 8H), 1.71 (s, 6H).

化合物 7.1 (5,5-二氟-10-(4-羥基-2,6-二甲基苯基)-1,3,7,9-四甲基-5H-4l4,5l4-二吡咯并[1,2-c:2',1'-f][1,3,2]二氮雜硼雜苯-2,8-二腈)：

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] borophen-2,8-dinitrile):

Compound 7.1.1 ( cyano -2,4 -dimethylpyrrole ) : Step 1: Add 7.6 mL of 25% HBr/AcOH slowly 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. Then, 200 mL of diethyl ether was added to the solution to obtain a white precipitate. The precipitate was filtered to obtain 18.03 g of glycine N' -methoxy- N' -formamide hydrobromide with a yield of 100%. 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: Dissolve 14.85 g of 3-aminocrotononitrile (180.8 mmol) and 17.95 g of glycine N' -methoxy- N' -methylamide hydrobromic acid dissolved in 1 L of dry ethanol A solution of the salt (90.4 mmol) 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 obtain 16.71 g of white solid. This solid can be 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: Under a nitrogen atmosphere, add 7.5 mL of 3.0 M MeMgBr in Et 2} O to a solution containing 3.82 g of the white powder (21.2 mmol) of step 2 dissolved in 150 mL of dry THF at -10°C (1.1 equivalent). The solution was stirred for 50 minutes. Next, 15 mL of 3.0 M MeMgBr in Et ₂ O solution (2.1 equivalents) was added at -10°C under a nitrogen atmosphere and stirred for another 2 hours. After this, the solution was quenched with 200 mL of water, and extracted with AcOEt. The organic layer was washed with brine, and dried _{over Na 2} SO _4. Filter and evaporate in vacuo. The product is a yellow solid, which can be used in step 4 without further purification.

Step 4: To a slurry containing 2.67 g of the yellow solid (19.3 mmol) from step 3 in 75 mL EtOH was added 273 mg NaOEt (4.01 mmol, 0.2 equivalent). The slurry was stirred at room temperature for 30 minutes. Then, 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 MgSO ₄ . Filter, evaporate in vacuo, and purify the filtrate by silica gel flash chromatography (n-hexane: AcOEt 3:1 as the eluent). Obtained 2.09 g (90%) of 3-cyano-2,4-dimethylpyrrole, compound 7.1.1, as a white solid. LCMS (APCI+): _{calculated value for C 7} H ₉ N ₂ (M+H)=121; ¹ H NMR (CDCl3) δ 8.06 (bs, 1H), 6.37 (1H, s), 2.37 (s, 3H), 2.13 (s, 3 H)), 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) is synthesized by a two (2) step process: Step 1: Under argon atmosphere, 1.12 g 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. Remove TFA and solvent under reduced pressure. The crude product can be used in step 2 without further purification. LCMS (M+H=373).

Step 2: Add 8 g of DDQ (35.2 mmol) to the solution containing the crude product of step 1 _{dissolved in 50 mL CHCl 3 and 5 mL EtOH.} The solution was stirred at room temperature for 1 hour. The solvent was removed under reduced pressure. The dark residue was re-dissolved in 50 mL CHCl ₃ and passed through a short silica gel column using CH ₂ Cl ₂ /EtOAc (1:1) as the eluent to obtain 2.35 g of compound 7.1.2 as an off-white solid. The total yield of the two steps is 85%. LCMS (APCI+): _{calculated value for C 23} H ₂₃ N ₄ O (M+H)=371; actually measured value: 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] diazaborobenzene-2,8-dinitrile): Add 2.35 g of compound 15.2 [ (Z)-5-((4-cyano-3,5-dimethyl-2H-pyrrol-2-ylidene)-(4-hydroxy-2,6-dimethylphenyl)methyl)- To a solution of 2,4-dimethyl-1H-pyrrole-3-nitrile] (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 NaOH aqueous solution (1M) was added to form an aqueous layer, which was separated. The aqueous layer was neutralized with 4N HCl aqueous solution, and then extracted with EtOAc. The combined organic layer was dried over MgSO ₄ and the solvent was removed. The residue was chromatographed on a silica gel column using hexane/EtOAc (1:1) as the eluent to obtain 1.05 g of product (39% yield). LCMS (APCI+): _{calculated value of C 23} H ₂₂ BF ₂ N ₄ O (M+H) = 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 ) 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] dinitrogen borane-10-yl) -3,5-dimethylphenyl): stir bar was charged in a 40 mL screw cap vial, 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 anhydrous dichloromethane (20 mL) was added. Diisopropylcarbodiimide (0.300 mmol, 47 uL) was added, and the reaction was stirred at room temperature under argon overnight. The next morning, anhydrous tetrahydrofuran (10 mL) was added and sonicated for 30 seconds. Another portion of compound 2.1 was added and stirred at 50°C overnight 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 product-containing fractions were evaporated to dryness to obtain 21 mg of PLC-7 (36% yield). MS (APCI): _{the calculated value of the chemical formula C 75} H ₆₀ BF ₂ N ₉ O ₂ (M-) = 1167; the measured value: 1167.

化合物 8.1 (4,7- 二溴 -2-(4- 氟苯基 )-2H- 苯并 [d][1,2,3] 三唑 ) ：

Example 2.8 : PLC-8

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

Step 1 : Add potassium monopersulfate (78.88 g, 127.96 mmol) to a mixture of 2-nitroaniline (10.58 g, 76 mmol) in H ₂ O (210 mL) and DCM (590 mL) , And the resulting mixture was stirred at 40°C for 48 hours. After cooling to room temperature, the reaction was separated. The aqueous layer was extracted again with DCM (150 mL×2), the DCM layers were combined, washed with 1N HCl aqueous solution, water and brine, then dried over MgSO ₄ and concentrated to dryness. The brown solid was ground into a powder with EtOH, filtered, and then air-dried to obtain 6.61 g of a light brown solid product. The yield was 57%. The product was used in the next step without further purification. LCMS (APCI+): _{calculated value of M+ of formula C 6} H ₄ N ₂ O ₃ : 152.11; measured value: 152

Step 2 : A mixture of 1-nitro-2-nitrosobenzene (1.4 g, 9.2 mmol) and 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 with water several times, and then dried to dryness in a vacuum oven to obtain 2.0 g of a light brown solid product. The yield was 89%. The product was used in the next step without further purification. LCMS (APCI+): _{calculated value of M+ of formula C 12} H ₈ FN ₃ O ₂ : 245.21; actually measured value: 245.

Step 3 : Add formamidine sulfinic acid (2.9 g, 26.89 mmol) to (E/Z)-1-(4-fluorophenyl)-2-(2-nitrophenyl)diazene (2.0 g , 8.15 mmol) in EtOH (50 mL), then 4 N NaOH aqueous solution (42 mL) was added, and the resulting mixture was stirred at 85°C for 16 hours. After cooling to room temperature, the solution was poured into ice water, the brown solid was collected by filtration, the product was washed with water several times, and then dried to dryness in a vacuum oven to obtain 1.61 g of a light brown solid product. The yield was 93%. The product was used in the next step without further purification. LCMS (APCI+): _{calculated value of M+ of formula C 12} H ₈ FN ₃ : 213.22; found value: 213. ¹ H NMR (400 MHz, CDCl3): 8.33 (d, J=9.16 Hz, 2H), 7.92 (d, J=9.5Hz, 2H), 7.42 (d, J= 9.9 Hz,2H), 7.24 (d, J= 2.92 Hz, 2H),

Step 4 : Add bromine (0.93 mL, 18.16 mmol) dropwise to 2-(4-fluorophenyl)-2H-benzo[d][1,2,3]triazole (1.55 g, 7.26 mmol) in 48 % HBr (20 mL), the resulting mixture was stirred at 130°C for 16 hours. After cooling to room temperature, the solution was decanted and discarded; the remainder in 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 MgSO _4, and concentrated. The filtrate was concentrated to dryness. The crude product was purified by SiO ₂ column chromatography and eluted with hexane:ethyl acetate (95:5) to obtain 1.96 g of compound 8.1. The yield was 73%. LCMS (APCI+): _{calculated value of M+ of formula C 12} H ₆ Br ₂ FN ₃ : 371.01; actually measured value: 371. ¹ H NMR (400 MHz, CDCl3): 8.41 (d, J=9.2 Hz, 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 filled with a stir bar, and equipped with a fin condenser and a gas adapter. The flask was flushed with argon. Compound 8.1 [4,7-二] was added to the flask Bromo-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). Heat the flask to 45°C in a heating block and bubbling with argon for 30 minutes. Then add (4-(diphenylamino)phenyl) while bubbling with argon Boric acid (13.8 mmol, 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 increase the temperature of the heating block to 110°C. Stir and heat at this temperature overnight. The reaction mixture was processed and flash chromatographed on silica gel (100% hexane (1 CV) à 30% toluene/hexane (0 CV) à 100% toluene ( 10 CV)) Purification. The product-containing fractions were evaporated to dryness to obtain 546 mg of compound 8.2 (yield 25%). MS (APCI): chemical formula C ₄₈ H ₃₄ FN ₅ (M-) calculated value = 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 -oxobutyric acid methyl ester ) : Put a stir bar into a 250 mL 2-neck round bottom flask, And equipped with finned condenser and gas adapter. The flask was flushed with argon. Compound 8.2 (0.780 mmol, 546 mg), anhydrous dichloromethane (100 mL), ZnCl ₂ (1.0 M Et ₂ O solution, 2.34 mmol, 2.34 mL) were added to the flask under stirring, and then 4-chloro Methyl-4-oxobutyrate (2.34 mmol, 0.288 mL). The reaction was stirred at room temperature under argon for 30 minutes and then heated to 45°C overnight. The 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 at 65°C for 3 hours. Additional methyl 4-chloro-4-oxobutanoate (2.34 mmol, 0.288 mL) was added, and heating was continued at 65°C for 7 hours. The reaction mixture was cooled to room temperature, evaporated to dryness, and purified by flash chromatography (100% DCM (1 CV)→10% EtOAc/DCM (10 CV)) on silica gel. The product-containing fractions were evaporated to dryness to obtain 160 mg of compound 8.3 (yield 25%). MS (APCI): _{The calculated value of the chemical formula C 53} H ₄₀ FN ₅ O ₃ (M-)=813; the measured value: 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 ) : Put compound 8.3 (0.197 mmol, 160 mg) in a 40 mL screw cap vial and stir Great. Flush the vial with argon. Anhydrous dichloromethane (10 mL) and trifluoroacetic acid (10 mL) were added to the vial. 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 that there was no more starting material. The crude reaction mixture was evaporated to dryness and purified by flash chromatography (100% DCM isocratic) on silica gel. The product-containing fractions were evaporated to dryness to obtain 140 mg of compound 8.4 (yield 89%). MS (APCI): _{The calculated value of the chemical formula C 53} H ₄₂ FN ₅ O ₂ (M-)=799; the measured value: 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 filled with a stir bar and equipped with a finned condenser And gas adapter. The flask was flushed with argon. Compound 8.4 (0.174 mmol, 139 mg) was added to the flask, 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 under argon in a heating block with stirring at 115°C overnight. The reaction mixture was cooled to room temperature, and water (10 mL) was added. Add trifluoroacetic acid until the pH is about 1. The reaction was evaporated to dryness. The dichloromethane soluble part was evaporated to dryness to obtain compound 8.5 in a quantitative yield. MS (APCI): _{The calculated value of the chemical formula C 52} H ₄₀ FN ₅ O ₂ (MH)=784, the measured value: 784.

PLC-8 (10-(4-((4-(4-((4-(7-(4-( diphenylamino ) phenyl )-2-(4- fluorophenyl )-2H- benzene And [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- two-pyrrolo [1,2-c: 2 ', 1'-f] [1,3,2] diazepin Borrabenzene- 2,8 -dicarboxylic acid dibenzyl ester ) : A 250 mL 2-neck round bottom flask is equipped with a finned condenser, a stir bar and a 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 anhydrous dichloromethane (20 mL) was added. Diisopropylcarbodiimide (0.300 mmol, 47 uL) was added, and the reaction was stirred at room temperature under argon overnight. The crude product was purified by flash chromatography on silica gel (80% DCM/hexane (1 CV)→100% DCM (5 CV)→100% DCM (isocratic)). The product-containing fractions were evaporated to obtain 63 mg of PLC-8 (90% yield). MS (APCI): _{the calculated value of the chemical formula C 89} H ₇₃ BF ₃ N ₇ O ₆ (M-)=1403; the measured value: 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).

PLC-9 (4-(4-((4-(7-(4-( 二苯基胺基 ) 苯基 )-2-(4- 氟苯基 )-2H- 苯并 [d][1,2,3] 三唑 -4- 基 ) 苯基 )( 苯基 ) 胺基 ) 苯基 ) 丁酸 4-(2,8- 二氰基 -5,5- 二氟 -1,3,7,9- 四甲基 -5H-4l4,5l4- 二吡咯并 [1,2-c:2',1'-f][1,3,2] 二氮硼烷 -10- 基 )-3,5- 二甲基苯酯 ) ： 在250 mL的2頸圓底燒瓶裝配帶翅片的冷凝器、攪拌棒及氣體適配器。將燒瓶用氬氣沖洗，加入化合物7.1 (0.055 mmol，35 mg)及化合物8.5 (0.050 mmol，39 mg)，以及DMAP:pTsOH 1:1鹽(0.200 mmol，59 mg)。用氬氣沖洗小瓶，且加入無水二氯甲烷(20 mL)。加入二異丙基碳二亞胺(0.300 mmol，47 uL)，且將反應在氬氣下在室溫下攪拌隔夜。藉由在矽膠上進行快速層析法(80% DCM/己烷(1 CV)à100% DCM (5 CV)à100% DCM (等度))來純化粗產物。將含有產物之級分蒸發至乾燥，得到39 mg (產率為59%)。MS (APCI)：化學式C₇₅ H₅₉ BF₃ N₉ O₂ (M-)之計算值=1185；實測值：1185。¹ H NMR (400 MHz, 四氯乙烷-d₂ ) 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, 1.4 Hz, 3H), 7.06 (s, 2H), 2.79-2.72 (m, 8H), 2.67 (t,J = 7.5 Hz, 2H), 2.13 (s, 8H), 1.63 (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- -5H-4l4,5l4- two-tetramethyl-pyrrolo [1,2-c: 2 ', 1'-f] [1,3,2] dinitrogen borane-10-yl) -3,5 - dimethylphenyl): 2-necked round bottom flask equipped with a condenser fins 250 mL of stirring rod and a 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 anhydrous dichloromethane (20 mL) was added. Diisopropylcarbodiimide (0.300 mmol, 47 uL) was added, and the reaction was stirred at room temperature under argon overnight. The crude product was purified by flash chromatography on silica gel (80% DCM/hexane (1 CV)→100% DCM (5 CV)→100% DCM (isocratic)). The product-containing fractions were evaporated to dryness, yielding 39 mg (59% yield). MS (APCI): _{The calculated value of the chemical formula C 75} H ₅₉ BF ₃ N ₉ O ₂ (M-)=1185; the measured value: 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, 1.4 Hz, 3H), 7.06 (s, 2H), 2.79-2.72 (m, 8H), 2.67 (t, J = 7.5 Hz, 2H), 2.13 (s, 8H), 1.63 (s, 6H).

Example 3 Manufacture of a color conversion film A glass substrate was essentially prepared in the following manner. A 1.1 mm thick glass substrate measuring 1 inch × 1 inch is cut into a certain size. Then the glass substrate was 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. Then the glass substrate was immersed in acetone and sonicated for about 1 hour. The glass was then taken out of the acetone bath and dried with nitrogen at room temperature.

Preparation of poly(methyl methacrylate) (PMMA) (the average molecular weight measured by GPC purchased from MilliporeSigma, Burlington, MA, USA is 120,000) 20 weight of copolymer in cyclopentanone (purity of 99.9%) % Solution. The prepared copolymer was stirred at 40°C overnight. [PMMA] CAS: 9011-14-7; [Cyclopentanone] CAS: 120-92-3

In a sealed container, add the 20% PMMA solution (4 g) prepared above to 3 mg of the photoluminescent composite prepared as described above, and mix for about 30 minutes. Then the PMMA/phosphor solution was spin-coated on the prepared glass substrate at 1000 RPM for 20 seconds, and then spin-coated on the prepared glass substrate at 500 RPM for 5 seconds. The resulting wet coating has a thickness of about 10 μm. Before spin coating, cover the sample with aluminum foil to prevent the sample from being exposed to light. Three samples were prepared in this way, and the emission/FWHM and quantum yield were measured for each of the three samples. The spin-coated sample was baked in a vacuum oven at 80°C for 3 hours to evaporate the remaining solvent. The thickness of the dried coating is about 2 μm.

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

Use a Fluorolog spectrofluorometer (Horiba Scientific, Edison, NJ, USA) to measure the fluorescence spectrum of the 1 inch × 1 inch film sample prepared as described above. The excitation wavelength of the Fluorolog spectrofluorometer is set to the corresponding maximum absorption wavelength . The maximum emission and FWHM are shown in Table 1.

Quantarus-QY spectrophotometer (Hamamatsu, Campbell CA, USA) was used to measure the quantum yield of the 1 inch × 1 inch sample prepared as described above. The Quantarus-QY spectrophotometer was excited at the corresponding maximum absorption wavelength. . 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. Table 1.

FIG. 1 is a graph depicting the absorption spectrum and emission spectrum of an embodiment of the photoluminescent composite PLC-1. Figure 2 absorption spectra of the embodiment and a graph depicting the emission spectra of the photoluminescent a composite of PLC-5.

Claims (22)

A photoluminescent composite, the photoluminescent composite comprising: a blue light-absorbing azole derivative; a linking group, the linking group comprising a non-substituted ester or a substituted ester, wherein the linking group shares the same The blue light-absorbing azole derivative and the BODIPY moiety are valently connected; 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, a substituted aryl group, or the linking group; wherein the azole derivative absorbs the first excitation wavelength The light energy and transfer energy to the BODIPY part, wherein the BODIPY part absorbs the energy from the azole derivative and emits light energy of a second higher wavelength. Such as the photoluminescent composite of claim 1, wherein the BODIPY part has the following general formula:

, Wherein R ¹ and R ^{6 are} independently H, alkyl, alkenyl, alkynyl or alkoxy-3-oxypropen-1-yl; wherein R ³ and R ^{4 are} independently H or C ₁ -C ₂ Alkyl; 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 joined together to form another monocyclic ring Hydrocarbon ring structure or polycyclic hydrocarbon ring structure; wherein R ⁴ and R ⁵ can be connected together to form another monocyclic hydrocarbon ring structure or polycyclic hydrocarbon ring structure; wherein R ⁷ and R ^{8 are} independently H or methyl; And L is the linking group. Such as the photoluminescent composite of claim 1, wherein the BODIPY part has the following general formula:

, Wherein R ¹ and R ^{2 are} connected together to form another polycyclic hydrocarbon ring structure; wherein R ⁵ and R ^{6 are} connected together to form another polycyclic hydrocarbon ring structure; wherein R ⁷ and R ^{8 are} independently H or Methyl; and L is the linking group. 2 or 3 photoluminescent composite, where Z is S. The photoluminescent composite of 2 or 3, wherein Z is NR ¹⁰ and R ¹⁰ is a substituted phenyl group. Such as the photoluminescent composite of claim 5, wherein R ¹⁰ is

. The photoluminescent composite 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. Such as the photoluminescent composite of claim 2, wherein R ¹ and R ⁶ are:

. The photoluminescent composite of 2 or 3, wherein the linking group is:

. The photoluminescent composite of 2 or 3, wherein the linking group is:

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

. A color conversion film, which includes: Transparent substrate layer; A color conversion layer, wherein the color conversion layer includes a resin matrix; and A photoluminescent composite, wherein the photoluminescent composite comprises a photoluminescent compound as claimed in claim 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 or 13, and the light The luminescent compound is dispersed in the resin matrix. The color conversion film of claim 14, wherein the color conversion film also contains a singlet oxygen quencher. The color conversion film of claim 14 or 15, wherein the color conversion film also contains a radical scavenger. Such as the color conversion film of claim 14 or 15, wherein the thickness of the film is between 1 µm and 200 µm. The color conversion film of claim 14 or 15, wherein the film absorbs light in the wavelength range of about 400 nm to about 480 nm and emits light in the wavelength range of about 510 nm to about 560 nm. The color conversion 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. The color conversion film of claim 14 or 15, wherein the emission quantum yield is 70% or more. A backlight unit comprising the color conversion film of claim 14, 15, 16, 17, 18, 19 or 20. A display device including a backlight unit as claimed in claim 21.

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