TW202132539A - 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 moiety, 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 for a color conversion film, and relates to a backlight unit and a display device including the above-mentioned backlight unit.

In color reproduction, the color gamut (gamut or 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 monitor. The Adobe TM RGB is a wide color achieved by using pure spectral primary colors. The color space of the field. It is believed that devices that can provide a wider color gamut may 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 current light emitting diode (LED) is obtained by exciting a green phosphor, a red phosphor or a yellow phosphor from a blue light source to obtain a white light source. However, the current full width half maximum (FWHM) (full width half maximum) of the emission peaks of the current green phosphors and red phosphors is very large, usually greater than 40 nm, which results in the overlap of the green and red spectra and prevents each color from being completely distinguished from each other. Separate. Such overlap can lead to poor color performance 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, non-cadmium-based quantum dots have very low efficiency in converting blue LED light into green and red light. 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.

A novel method to solve the problems presented by the use of quantum dots involves the use of boron dipyrromethene (BODIPY) compounds as luminescent materials instead of quantum dots.

The photoluminescent compounds described herein can be used to improve the contrast between distinguishable colors in televisions, computer monitors, smart devices, and any other devices that utilize color displays. The photoluminescent composite of the present invention provides a novel color conversion composite, which has good blue light absorbance and narrow emission band width, wherein the full width at half width [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 wavelength higher than the first wavelength. The photoluminescent composite disclosed in the present invention can be used together with a color conversion film used in a light-emitting device. The color conversion film of the present invention reduces color degradation by reducing the overlap in the color spectrum, thereby resulting in high-quality color reproduction.

Some embodiments include a photoluminescent composite, the photoluminescent composite described above comprising: a donor chromophore; an acceptor chromophore; and a linker complex. Some photoluminescent composites are represented by Formula I: A—(L—D) _1-3 [Formula I].

[式II]。In some embodiments, the donor chromophore or D absorbs light at blue wavelengths and emits excitation energy. The above-mentioned donor chromophore may comprise a perylene derivative of the following formula:

[Formula II].

In some embodiments, R ⁸ , R ¹⁰ and R ¹¹ may be selected from H or -CF ₃ . In some embodiments, R ⁹ is H.

[式III]， 在一些實施方式中，R'獨立地為H、-CH₃ 、F或CF₃ ；R''為-H、或連接至L—D之鍵；R¹ 及R² 獨立地為H或-CH₃ ；R³ 及R⁴ 獨立地為H、F、Br、-CF₃ 、視情況經1個或2個-CH₃ 、-F、-CF₃ 取代之苯基、或-L—D基團；X為-CH₂ -、-CH₂ CH₂ -、-CH₂ CH₂ CH₂ -、-C(R^a )₂ -、-CHC(R^a )-、-C(=O)-、-O-、-S-、-C(Ar)₂ -、-C(CH₂ Ar)₂ -、螺環-環烷基基團或芳族螺環-多環基團，其中R^a 為C₁ -C₄ 烷基並且其中Ar為芳基基團或雜芳基基團；並且L為視情況經取代之C₄ -C₇ 酯或C₃ -C₅ 酮酯。In some embodiments, the acceptor chromophore or A emits light at a red wavelength. The above-mentioned acceptor chromophore may comprise a BODIPY derivative of the following formula:

[Formula III], in some embodiments, R'is independently H, -CH ₃ , F or CF ₃ ; R ″ is -H or a bond connected to LD; R ¹ and R ^{2 are} independently Is H or -CH ₃ ; R ³ and R ^{4 are} independently H, F, Br, -CF ₃ , phenyl substituted with 1 or 2 -CH ₃ , -F, -CF _{3, or-} L—D group; X is -CH ₂ -, -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -C(R ^a ) ₂ -, -CHC(R ^a )-, -C(= O)-, -O-, -S-, -C(Ar) ₂ -, -C(CH ₂ Ar) ₂ -, spiro-cycloalkyl group or aromatic spiro-polycyclic group, wherein Ra is ^a C ₁ -C ₄ alkyl group and wherein Ar is an aryl group or a heteroaryl group; and L is an optionally substituted C ₄ -C ₇ ester or C ₃ -C ₅ keto ester.

In some embodiments, the acceptor chromophore absorbs the excitation energy emitted by the donor chromophore, wherein the acceptor chromophore subsequently emits light of a second wavelength, and the light of the second wavelength has a wavelength greater than that of blue light. High-wavelength light. In some embodiments, the acceptor chromophore emits red wavelength light. The linker complex connects the donor chromophore with the acceptor chromophore.

In some embodiments, the emission quantum yield of the photoluminescent composite is greater than 80%.

In some embodiments, the photoluminescent composite may have an emission band with a full width at half width [FWHM] of at most 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 excitation peak of the BODIPY part.

Some embodiments include a color conversion film, which may include: a transparent substrate layer; and a color conversion layer. In some embodiments, the color conversion layer may include a resin matrix and at least one photoluminescent compound dispersed in the resin matrix. In some embodiments, the thickness of the color conversion film may be between 1 µm and about 200 µm. In other embodiments, the color conversion film may include a singlet oxygen scavenger. In some examples, the color conversion film may include a radical scavenger. Another embodiment includes a color conversion film that can absorb blue light in the range of 400 nm to about 480 nm and emit red light in the wavelength range of 575 nm to about 650 nm. In some embodiments, the color conversion film may also include a transparent substrate layer. Some embodiments include a color conversion film that has at least 80% light stability after being exposed to blue light with a peak wavelength of 465 nm for 165 hours. Other embodiments include a color conversion film that has at least 75% light stability after being exposed to blue light with a peak wavelength of 465 nm for 330 hours. In some embodiments, the transparent substrate layer of the color conversion film includes two opposing surfaces, and the color conversion layer is disposed on one of the opposing surfaces.

Some embodiments include a method for preparing a color conversion film, the method comprising: dissolving a resin matrix and a photoluminescent composite in a solvent; and applying the mixture on one of the opposite surfaces of a transparent substrate.

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

Some embodiments describe a display device that includes the backlight unit described herein.

These and other embodiments are described in more detail below.

Cross-reference of related applications. This application requires the rights of U.S. Provisional Application No. 62/962,626 filed on January 17, 2020 and U.S. Provisional Application No. 63/008,284 filed on April 10, 2020, all of the above-mentioned U.S. Provisional Application The content is incorporated into this article by reference.

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

The use of the term "may" should be interpreted as a shorthand for "to" or "not to", or alternatively to "do" or "not do" or "will" or "will not". For example, the expression "the alkyl group may be substituted" should be interpreted as, for example, "in some embodiments, the alkyl group is substituted, and in some embodiments, the alkyl group is not substituted." In another example, the expression "photoluminescent composite can enhance contrast" should be interpreted as, for example, "in some embodiments, the photoluminescent composite of the present invention does enhance contrast. In some embodiments, the present invention The photoluminescent composite does not enhance contrast." In another example, the expression "the color conversion film may also include a second photoluminescent composite" should be interpreted as, for example, "In some embodiments, the color conversion film will include a second photoluminescent composite. In some embodiments, , The color conversion film will not also contain the second photoluminescent composite.”

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

The term "alkyl" group as used herein refers to a hydrocarbyl group without double or triple bonds. The "olefin moiety" refers to a group having at least one carbon-carbon double bond, and the "alkyne" moiety refers to a group having at least one carbon-carbon triple bond. The alkyl, alkene, or alkyne moiety can be linear, branched, or cyclic.

The alkyl moiety can have 1 to 6 carbon atoms (regardless of where it appears herein, a numerical range such as "1 to 6" refers to each integer in the given range: for example, "1 to 6 carbon atoms""Means that the alkyl group can have 1, 2, 3, 4, 5 or 6 carbon atoms, but this definition also covers the occurrence of the term "alkyl" without a specified numerical range. As specified herein The alkyl group of a 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, secondary 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 but Not limited to methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl, hexyl, vinyl, propenyl, butenyl, cyclopropyl, cyclobutyl , Cyclopentyl, cyclohexyl, etc.

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 a heteroatom. An example of a heteroalkyl group is "alkoxy", and "alkoxy" as used herein refers to alkyl-O- (e.g., methoxy, ethoxy, etc.).

The term "heteroatom" as used herein refers to nitrogen (N), oxygen (O), or sulfur (S).

The term "aromatic" refers to a planar ring with a delocalized π electron system containing 4n+2 π electrons, where n is an integer. Aromatic rings can be formed of, for example, 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、

[六氫化茚]、

[1,2,3,4-四氫化萘]、

[1,2,3,3a-四氫并環戊二烯]、

[9H -茀]、

螺環[環戊烷-1,9'-茀]等。The term "hydrocarbon ring" refers to a monocyclic or polycyclic group that contains only carbon and hydrogen and may be saturated, partially saturated, or fully 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],

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

[ 9H -茀],

Spiro ring [cyclopentane-1,9'-茀] and so on.

The term "aryl" as used herein refers to an aromatic ring in which every atom forming the ring is a carbon atom. Aryl groups can be substituted or unsubstituted. Examples of aryl groups include, but are not limited to, phenyl, naphthyl, phenanthryl, tetraphenyl, stilbene, pyrenyl, and the like.

The term "heteroaryl" refers to an aryl group that includes one or more ring heteroatoms selected from nitrogen, oxygen, and sulfur, wherein the heteroaryl group has 4 to 10 atoms in its ring system. It should be understood that a 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, 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 to be part of a larger structure, between two atoms, to The chemical bond of the two parts.

The term "portion" as used herein refers to a specific segment or functional group of a molecule. The chemical moiety is often thought of as a chemical entity embedded in or attached to a molecule.

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

The term "ester" refers to a chemical moiety having the formula -C(=O)OR, where R is selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl (bonded by ring carbon) and heterocycle (by Ring carbon bonding). Any hydroxyl or carboxyl side chain on the compounds described herein can be esterified. The procedures and specific groups for preparing such esters are known to those skilled in the art and can be easily found in reference sources.

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

As used herein, the term "ketone" refers to a chemical moiety containing a carbonyl group (C=O) attached to two alkyl or aryl groups, where the general formula is RC(=O)R', where the term alkane Group and aryl are as defined herein.

。The term "BODIPY" or "BODIPY derivative" as used herein refers to a chemical moiety with the following general structure:

.

BODIPY can be composed of a dipyrromethene group compounded with a disubstituted boron atom (usually a BF _{2 unit).} The IUPAC name of the general core structure of BODIPY is 4,4-difluoro-4-bora-3a,4a-diaza-s-indase.

。The term "perylene" or "perylene derivative" refers to a chemical moiety with the following general structure:

.

The present invention includes a photoluminescent composite that absorbs light energy at a first wavelength and emits light energy at a second higher wavelength. The photoluminescent composite of the present invention may comprise a donor chromophore, wherein the donor chromophore can absorb blue light (wavelength from 400 nm to 480 nm) and release excitation energy in response thereto; the acceptor chromophore, the The acceptor chromophore may comprise a boron dipyrromethene (BODIPY) derivative, which can absorb the excitation energy released from the donor chromophore, wherein the acceptor chromophore can subsequently emit light of a second wavelength , The light of the second wavelength may be light having a wavelength higher than the wavelength of blue light; and a linker complex that can connect the donor chromophore and the acceptor chromophore together. The photoluminescent compound described in this article can be incorporated into the color conversion film, thereby greatly improving the distinguishability between the colors in the red, green and blue (RGB) color gamut, resulting in increased contrast and higher color performance quality.

In some embodiments, the photoluminescent complex includes a donor chromophore, an acceptor chromophore, and a linker complex. The donor chromophore and the acceptor chromophore are connected to create a spatial relationship, which is completed by the linker complex. In some embodiments, the donor chromophore can absorb blue wavelength light and then release excitation energy. The acceptor chromophore can absorb the excitation energy released by the donor chromophore, and then the acceptor chromophore can emit light of a second wavelength, where the light of the second wavelength can be light with a higher wavelength than blue light . In some embodiments, the acceptor chromophore emits red light. It is believed that the energy transfer from the donor chromophore to the acceptor chromophore occurs through fluorescence resonance energy transfer (FRET).

式1A                  式IB                   式IC； 其中A為受體發色團，L為連接基複合物，並且D為供體發色團。The photoluminescent complex can be represented by formula I: A—(L—D) _1-3 , which means that there may be 1, 2, or 3 L—D groups attached to the acceptor chromophore A, for example in In the following formulas IA, IB and IC: A—L—DD—L—A—L—D

Formula 1A Formula IB Formula IC; where A is the acceptor chromophore, L is the linker complex, and D is the donor chromophore.

[式II]。In some embodiments, the donor chromophore (D) may comprise a perylene derivative of the following formula;

[Formula II].

In some embodiments, R ⁸ , R ¹⁰ and R ¹¹ may be hydrogen (H) or trifluoromethyl (CF3). In some embodiments, R ⁹ is H. In some embodiments, R ⁸ is H. In some embodiments, R ⁸ is CF ₃ . In some embodiments, R ¹⁰ is H. In some embodiments, R ¹⁰ is CF ₃ . In some embodiments, R ¹¹ is H. In some embodiments, R ¹¹ is CF ₃ . In some embodiments, R ⁸ , R ¹⁰ and R ¹¹ are all H. In some embodiments, R ⁸ , R ¹⁰ and R ¹¹ are all CF ₃ .

Some embodiments include a photoluminescent composite, wherein the photoluminescent composite includes a donor chromophore that absorbs light of blue wavelengths. In some embodiments, the maximum blue light absorbance of the donor chromophore can be 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, about 430 nm. nm to about 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 any range defined by these wavelength. In some embodiments, the maximum absorbance peak of the photoluminescent composite may be about 450 nm. In other embodiments, the maximum peak absorbance of the donor chromophore may be about 405 nm. In another embodiment, the maximum absorbance peak of the donor chromophore may be about 480 nm.

[式III]， 關於任何相關之結構表示，例如式III，每個R'為H、甲基(-CH₃ )、F或CF₃ 。在一些實施方式中，一個R'為H。在一些實例中，兩個R'都為H。在一些實施方式中，一個R'為CH₃ 。在一些實例中，兩個R'都為CH₃ 。In some embodiments, the acceptor chromophore (A) may comprise a boron dipyrromethene (BODIPY) derivative. BODIPY derivatives can have the following general formula:

[Formula III], for any related structural representation, such as formula III, each R'is H, methyl (-CH ₃ ), F or CF ₃ . In some embodiments, one R'is H. In some instances, both R'are H. In some embodiments, one R′ is CH ₃ . In some instances, both R'are CH ₃ .

Regarding any related structural representations, for example, Formula III, R" is -H, or a bond connected to L-D, where L is a linking group and D is a donor chromophore.

Regarding any related structural representations, for example, Formula III, R ¹ and R ^{2 are} independently H or methyl (-CH ₃ ). In some embodiments, R ¹ is H. In some embodiments, R ¹ is CH ₃ . In some embodiments, R ² is H. In some embodiments, R ² is CH ₃ . In some embodiments, both R ¹ and R ² are H. In some embodiments, both R ¹ and R ² are CH ₃ .

Regarding any related structural representations, for example, formula III, R ³ and R ^{4 are} independently H, F, Br or -CF ₃ , as appropriate, benzene substituted with 1 or 2 -CH ₃ , -F, -CF ₃ Group, or -L-D group, where L is the linking group and D is the donor chromophore. In some embodiments, R ³ is H. In some embodiments, R ³ is F. In some embodiments, R ³ is phenyl, such as unsubstituted phenyl. In some embodiments, R ³ is phenyl substituted with -L-D. In some embodiments, R ⁴ is H. In some embodiments, R ⁴ is F. In some embodiments, R ⁴ is phenyl, such as unsubstituted phenyl. In some embodiments, R ⁴ is phenyl substituted with -LD. In some embodiments, both R ³ and R ⁴ are H. In some embodiments, both R ³ and R ⁴ are F. In some embodiments, R ³ and R ⁴ are both phenyl groups, such as unsubstituted phenyl groups. In some embodiments, both R ³ and R ⁴ are phenyl substituted with -LD.

。Regarding any related structural representations, for example, formula III, X is a bridging group connecting a phenyl aromatic ring and a pyrrole ring, such as an alkyl group, including -C _x H _2x -, where x is 1, 2, 3, 4, etc., For example -CH ₂ -, -C ₂ H ₄ , -CH ₂ CH ₂ CH ₂ -; -C(R ^a ) ₂ -; -CH ₂ C(R ^a ) _2- ; -C(=O)-;- O -; - S -; - C (Ar) 2 -; - C (CH 2 Ar) 2 -; spiro - cycloalkyl group; or an aromatic spiro - polycyclic group, wherein R ^a is C ₁ -C ₄ alkyl, and wherein Ar is an aryl or heteroaryl group. In some embodiments, X is -CH ₂ CH ₂ -. In some embodiments, X is -CH ₂ CH ₂ CH ₂ -. In some embodiments, X is

.

In some embodiments, when X is a spiro-cycloalkyl group, the aforementioned spiro-cycloalkyl group may include spiro-cyclopentane.

。In some embodiments, the BODIPY part or A can be:

.

In some embodiments, the photoluminescent composite comprises a linker complex or L, wherein the linker complex covalently connects the blue light-absorbing moiety (A) to the BODIPY light-emitting moiety (D). In some embodiments, the linker complex may include a single bond between the blue light absorbing moiety and the BODIPY moiety. In other embodiments, the linker complex may include substituted or unsubstituted ester groups. In some embodiments, the photoluminescent composite emits red light.

。Regarding any related structural representations, such as Formula I, Formula IA, Formula IB, or Formula IC, L is a linker complex that contains optionally substituted C ₂ -C ₇ esters or C ₃ -C ₅ Ketoester. In some embodiments, L is:

.

It is believed that the ester linking group helps to increase the distance between the blue light-absorbing portion of the perylene and the BODIPY portion, thereby generating through space energy transfer (FRET) instead of cross-bond energy transfer. As a result, the quantum yield of the photoluminescent composite is greater than 70%.

In one embodiment, the photoluminescent composite may have a high emission quantum yield. In some embodiments, the emission quantum yield can be greater than 50%, 60%, 70%, 80%, or 90%; and can be as high as or close to 100%. In some embodiments, the emission quantum yield may be greater than 50%, or 55%, or 60%, or 65%, or 70%, or 75%, or 80%, or 85%, or 90%, or 95% ; And can be as high as or close to 100%. In some embodiments, the emission quantum yield can be greater than 80% and can be as high as 100%. The emission quantum yield can be measured by dividing the number of emitted photons by the number of absorbed photons, which is equivalent to the emission efficiency of the light-emitting part. In some embodiments, the emission quantum yield of the absorbing light-emitting part can be greater than 75%, and can be as high as 100%. In some embodiments, the quantum yield can be greater than 0.75 (75%), 0.76 (76%), 0.77 (77%), 0.78 (78%), 0.79 (79%), 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%) and/or 0.95 (95%); and can be as high as or close to 1 (100%). The quantum yield in the film can be measured by a spectrophotometer, such as a Quantaurus-QY spectrophotometer (Humamatsu, Inc., Campbell, CA, USA).

In some embodiments, the photoluminescent composite has an emission band, which may have a full width at half width (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, and less than or equal to about 20 nm.

In some embodiments, the Stokes shift of the photoluminescent composite can be equal to or greater than 45 nm and up to 100 nm, up to 200 nm, or up to 300 nm. As used herein, the term "Stokes shift" refers to the distance between the excitation peak of the donor chromophore and the emission peak of the acceptor chromophore.

The photoluminescent composite of the present invention can have a tunable emission wavelength. By substituting different substituents for the BODIPY part of the acceptor chromophore, the emission wavelength can be tuned between 575 nm and 650 nm, or to any number defined by the range.

In some embodiments, the peak absorption maximum of the donor chromophore may be between about 400 nm and about 480 nm wavelength. In some embodiments, the peak absorption may be between 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. nm, about 425 nm to about 430 nm, about 430 nm to about 435 nm, about 435 nm, about 440 nm, about 440 nm to about 445 nm, about 445 nm, 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, about 470 nm to about 480 nm, or any number defined by these ranges.

In some embodiments, the emission peak of the photoluminescent composite may be between about 575 nm and about 650 nm wavelength. In some embodiments, the emission peak may be between 575 nm to about 580 nm, about 580 nm to about 585 nm, about 585 nm to about 590 nm, about 590 nm to about 595 nm, about 595 nm to about 600 nm, About 600 nm to about 605 nm, about 605 nm to about 610 nm, about 610 nm to about 615 nm, about 615 nm to about 620 nm, about 620 nm to about 625 nm, about 625 nm to about 630 nm, about 630 nm to about 635 nm, about 635 nm to about 640 nm, about 640 nm to about 645 nm, about 645 nm to about 650 nm, or any range defined by any of these equivalent values.

Other embodiments include photoluminescence complexes, in which the spatial distance between the donor chromophore and the acceptor chromophore is optimized by the linker complex to transfer the emission energy of the blue light-absorbing part to the luminescence of the BODIPY derivative part.

[式II]In some embodiments, the blue light-absorbing moiety can be a perylene derivative of formula I:

[Formula II]

For the perylene derivative of formula II, the perylene may include perylene, wherein R ⁸ , R ¹⁰ and R ¹¹ may be selected from hydrogen (H) or trifluoromethyl (CF ₃ ) . In some embodiments, R ⁹ is H.

The light stability (or durability) of organic compounds and composites is a very common problem. The light stability of organic photoluminescence composites is mainly due to the photooxidation process. It is believed that an electron-withdrawing group (or called an electron-accepting group) is added to the reaction site on the perylene structure. The above-mentioned electron-accepting group absorbs from the atomic group on the photoluminescence complex by the induction effect or the resonance effect. The electrons result in a lower HOMO/LUMO energy level, which is detrimental to the photo-oxidation of the photoluminescent complex.

The electron-accepting group may include a cyano group (-CN), a _{fluorine-containing alkyl group (for example, a trifluoromethyl group (-CF 3} )), or a fluorine-containing aryl group (for example, 4-(trifluoro (Methyl) phenyl group) because such groups are unlikely to be chemically decomposed.

In some embodiments, the perylene derivative can be attached to the second BODIPY derivative acceptor light-emitting moiety. In some embodiments, the linker complex and the second absorbing and luminescent complex may be covalently bonded to Formula I.

In some embodiments, the ratio between the blue light absorbing part and the BODIPY part may be 1:1. In some embodiments, the ratio between the blue light absorbing part and the BODIPY part may be 2:1. In some embodiments, the ratio between the blue light absorbing part and the BODIPY part may be 3:1.

。In some embodiments, the photoluminescent composite includes the structure shown below.

.

Some embodiments include a color conversion film that includes a transparent substrate layer and 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 includes dispersed The photoluminescent composite described above in a resin matrix. In some embodiments, the color conversion film can be described as comprising one or more of the photoluminescent composites described herein. In some embodiments, the color conversion film may include a photoluminescent composite having an absorbance of 400 nm to 480 nm light wavelength and an emission of 510 nm to 560 nm light wavelength. In some embodiments, the color conversion film may include a photoluminescent composite having an absorbance of 400 nm to 480 nm light wavelength and an emission of 575 nm to 650 nm light wavelength.

In some embodiments, the color conversion film may include a transparent substrate layer. The transparent substrate layer has two opposite surfaces, wherein the color conversion layer can be arranged on the surface of the transparent layer that will be adjacent to the light-emitting source and physically contact the above-mentioned surface. There is no particular limitation on the transparent substrate, and those familiar with this technology will be able to select a transparent substrate from among the transparent substrates used in this technology. 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 (polyhedroxy alkanoate), PHBV (poly(3-hydroxybutyrate-co-poly-3-hydroxyvalerate)), PBE (Polybutylene terephthalate) and PTT (polytrimethylene terephthalate). Any of the above resins may be corresponding/corresponding monomers and/or polymers.

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 be in physical contact with the above-mentioned 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 skilled in the art can determine which material and thickness to use as the supporting substrate.

Some embodiments include a color conversion film, wherein the film includes a color conversion layer. The color conversion layer may include a resin matrix and a photoluminescent composite (such as the photoluminescent composite described herein), and the resin matrix and the photoluminescent composite are dissolved in a solvent.

The resin matrix forms a continuous phase, and can contain materials with superior mold workability, heat resistance, and transparency. The above-mentioned resin matrix material may contain a polymer. To give a few examples, some non-limiting examples of polymers used in color conversion films include, but are not limited to, materials based on poly(meth)acrylic acid (such as polymethylmethacrylate (PMMA)), Polyester (PC) materials, polystyrene (PS)-based materials, polyarylene (PAR)-based materials, polyurethane-based materials, styrene-acrylonitrile (SAN)-based materials and polyvinylidene difluoride Vinyl (PVDF) material. The resin matrix is non-limiting, and those skilled in the art will be able to choose which polymer material will be used for their application.

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.

In some embodiments, the color conversion film may also include a second photoluminescent composite, wherein the second composite has an absorbance within a light wavelength of 400 nm to 470 nm and an emission within a light wavelength of 510 nm to 560 nm . In some embodiments, the color conversion film may also include a photoluminescent composite having an absorbance of 400 nm to 480 nm light wavelength and an emission of 575 nm to 650 nm light wavelength.

In some embodiments, the color conversion film also includes additives. Additives can be used to prevent the degradation of the photoluminescent composite and enhance the durability, that is, to inhibit the decrease in luminous intensity over time. In some embodiments, LA-57 is an effective additive.

In some embodiments, the color conversion film also includes a singlet oxygen quencher. The singlet oxygen quencher is a material that captures the singlet oxygen generated by the activation of light energy oxygen molecules and deactivates the singlet oxygen. The coexistence of the singlet oxygen quencher in the composition makes it possible to prevent the singlet oxygen from deteriorating the photoluminescent composite.

Singlet oxygen is known to be caused by the existence of electrons and energy exchange between perylene or BODIPY structure and ground state oxygen molecules. In the color conversion film of the present invention, the photoluminescent composite is excited by the excitation light and emits light having a wavelength different from the excitation light, thereby converting the light having one wavelength into a second higher wavelength. With each cycle of excitation light emission, the possibility of generating singlet oxygen increases due to the interaction between the generated excited state material and the oxygen molecules present in the composition. The possibility of collision between the photoluminescent composite and the singlet oxygen species increases, which leads to the deterioration of the photoluminescent composite. Some non-limiting examples of singlet oxygen quenchers include nickel additives such as nickel chloride, bis(acetone) nickel (II) (Ni(acac) ₂ , Millipore Sigma, Burlington, MA USA), nickel carbonate, etc. .

In some embodiments, the color conversion film may also include a free radical scavenger. In some embodiments, the free radical scavenger may include 1,4-diazabicyclo[2.22.]octane (DABCO, Millipore Sigma, Burlington, MA USA).

In some embodiments, the additives may include hindered light stabilizers. The hindered light stabilizer may include tertiary amines. Some non-limiting examples of tertiary amines include Si (2,2,6,6-tetramethyl-4-piperidinyl) 1,2,3,4,-butane tetracarboxylate (STAB LA-57 , Adeka Corporation, Arakawa, Tokyo, Japan), 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate (STAB LA-81, Adeka), 2,2,6,6 -Tetramethyl-4-piperidinyl methacrylate (STAB LA-87, Adeka), trimethylamine, N,N-diethylaniline, 1,2,2,6,6-pentamethylpiperidine , Bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, etc.

The color conversion film may be about 1 μm to about 200 μm thick. In some embodiments, the thickness of the color conversion film is about 1 µm to about 5 µm, about 5 µm to about 10 µm, about 10 µm to about 15 µm, about 15 µm to about 20 µm, about 20 µm to about 40 µm. µm, about 40 µm to about 80 µm, about 80 µm to about 120 µm, about 120 µm to about 160 µm, about 160 µm to about 200 µm, about 10 µm, or any thickness defined by the above range.

In some embodiments, the color conversion film can absorb light in the wavelength range of 400 nm to 480 nm, and can emit light in the range of about 575 nm to about 650 nm. In some embodiments, the color conversion film can absorb light in the wavelength range of 400 nm to 480 nm, and can emit light in the range of 510 nm to about 560 nm. In another embodiment, the color conversion film can absorb light in the range of 400 nm to about 480 nm, and can emit two higher wavelengths (510 nm to about 560 nm wavelength range and 575 nm to about 650 nm wavelength range , Or any combination thereof) of the light.

Some embodiments include a method for preparing a color conversion film, the method comprising: dissolving a resin matrix and at least one photoluminescent composite in a solvent, wherein the at least one photoluminescent composite is described above; and The mixture is applied to the surface of the transparent substrate.

In some embodiments, the method for preparing the color conversion film also includes dissolving the second photoluminescent composite, the second photoluminescent composite having an excitation wavelength of 400 nm to about 480 nm and an excitation wavelength of 510 nm to about 480 nm. Approximately 560 nm emission wavelength. In some embodiments, the second photoluminescent composite has an excitation wavelength of 400 nm to about 480 nm and an emission wavelength of 575 nm to about 560 nm.

In some embodiments, the method also includes dissolving the free radical scavenger in a solvent. The free radical scavenger may be 1,4-diazabicyclo[2.22.]octane (DABCO, Millipore Sigma).

In some embodiments, the method also includes dissolving the singlet oxygen quencher in a solvent.

Some embodiments include a backlight unit; the backlight unit may include the color conversion film described above.

Some embodiments include color conversion films with high light stability. In some examples, as measured by UV-vis 3600 (Shimadzu), the absorption at the peak absorption wavelength is measured before and after the color conversion film is exposed to LED light for 165 h, 330 h, and 500 h, respectively. And the remaining absorption (measured after each exposure time period) divided by the absorption before exposure indicates the light stability of the color conversion film. In some embodiments, the light stability is at least 80%, at least 82%, at least 85%, at least 90%, or at least 93%, and can be close to 100% after 165 hours of exposure. In other embodiments, the light stability is at least 75%, at least 77%, at least 80%, at least 85%, at least 90%, or at least 91%, and can be close to 100% after 330 hours of exposure.

Other embodiments may describe a display device, which may include the following backlight unit.

Unless otherwise specified, all numbers used in the specification and embodiments to indicate 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 attached embodiments are approximate values, and the above-mentioned approximate values can be changed according to the required 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 implementation, each numerical parameter should be explained at least based on the number of reported significant digits and by applying ordinary rounding techniques.

For the disclosed processes and/or methods, the functions performed in the above 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 type is only exemplary, and many other architectures that achieve the same or similar functionality can be implemented. Implementation

[式II]， 其中R⁸ 、R¹⁰ 及R¹¹ 選自H或CF₃ ，並且其中R⁹ 為H； 受體發色團，上述受體發色團包含二吡咯亞甲基硼(BODIPY)衍生物，其中上述受體發色團吸收由上述供體發色團發射之上述激發能量，其中上述受體發色團隨後發射第二波長之光，上述第二波長之光係具有比上述藍光波長更高之波長的光；以及 連接基複合物，上述連接基複合物用於將上述供體發色團與上述受體發色團連接起來； 並且其中上述光致發光複合物之發射量子產率大於80%。 Embodiment 1. A photoluminescent composite, the photoluminescent composite comprising: a donor chromophore, wherein the donor chromophore absorbs light of blue wavelength and emits excitation energy in response thereto, wherein the donor Chromophores include perylene derivatives of the following formula:

[Formula II], wherein R ⁸ , R ¹⁰ and R ^{11 are} selected from H or CF ₃ , and wherein R ⁹ is H; an acceptor chromophore, the aforementioned acceptor chromophore includes boron dipyrromethene (BODIPY) Derivatives, wherein the acceptor chromophore absorbs the excitation energy emitted by the donor chromophore, wherein the acceptor chromophore subsequently emits light of a second wavelength, and the light of the second wavelength is higher than the blue light Light with a higher wavelength; and a linker complex, wherein the linker complex is used to connect the donor chromophore and the acceptor chromophore; and wherein the emission quantum product of the photoluminescence complex The rate is greater than 80%.

[式III]， 其中R'獨立地為H、甲基基團(-CH₃ )、F或CF₃ ； R''為-H、或連接至L—D之鍵； R¹ 及R² 獨立地選自H或甲基(-CH₃ )； R³ 及R⁴ 獨立地為H、F、Br或-CF₃ 、視情況經1個或2個-CH₃ 、-F、-CF₃ 取代之苯基、或-L—D基團； X為連接苯基芳環及吡咯環之橋接基團；其中X為-CH₂ -、-CH₂ CH₂ -、-CH₂ CH₂ CH₂ -、-C(R^a )₂ -、-CHC(R^a )₂ -、-C(=O)-、-O-、-S-、-C(Ar)₂ -、-C(CH₂ Ar)₂ -、螺環-環烷基基團或芳族螺環-多環基團，其中R^a 為C₁ -C₄ 烷基並且其中 Ar為芳基基團或雜芳基基團； L為包含視情況經取代之C₄ -C₇ 酯或C₃ -C₅ 酮酯的連接基複合物；且 D為供體發色團。 Embodiment 2. The photoluminescent composite according to embodiment 1, wherein the BODIPY derivative has the following general formula:

[Formula III], wherein R'is independently H, a methyl group (-CH ₃ ), F or CF ₃ ; R" is -H, or a bond connected to LD; R ¹ and R ^{2 are} independently Ground is selected from H or methyl (-CH ₃ ); R ³ and R ^{4 are} independently H, F, Br or -CF ₃ , optionally substituted by 1 or 2 -CH ₃ , -F, -CF ₃ The phenyl group or the -L-D group; X is a bridging group connecting the phenyl aromatic ring and the pyrrole ring; wherein X is -CH ₂ -, -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH _2- , -C(R ^a ) ₂ -, -CHC(R ^a ) ₂ -, -C(=O)-, -O-, -S-, -C(Ar) ₂ -, -C(CH ₂ Ar) ₂ -, a spiro-cycloalkyl group or an aromatic spiro-polycyclic group, where Ra is ^a C ₁ -C ₄ alkyl group and where Ar is an aryl group or a heteroaryl group; L is A linker complex containing optionally substituted C ₄ -C ₇ esters or C ₃ -C ₅ keto esters; and D is the donor chromophore.

Embodiment 3. The photoluminescent composite according to embodiment 1, wherein when X forms a spiro-cycloalkyl group, the above-mentioned spiro-cycloalkyl group is spiro-cyclopentane.

Embodiment 4. The photoluminescent composite according to embodiment 1, wherein when X forms a spiro-polycyclic group, the above-mentioned spiro-polycyclic group is spiro-polycyclic.

。 Embodiment 5. The photoluminescent composite according to embodiments 1, 2, 3, and 4, wherein the above-mentioned C ₄ -C ₇ ester linking group has the following general formula:

.

。 Embodiment 6. The photoluminescent composite according to embodiments 1, 2, 3, and 4, wherein the above-mentioned C ₃ -C ₅ keto ester linking group has the following general formula:

.

。 Embodiment 7. The photoluminescent composite of Embodiments 1, 2, 3, 4, 5, and 6, wherein the photoluminescent composite is selected from one of the following structures:

.

Embodiment 8. 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 photoluminescent compound, wherein the at least one photoluminescence compound comprises According to the photoluminescent compounds of Examples 1, 2, 3, 4, 5, 6, and 7, the photoluminescent compound is dispersed in the resin matrix.

Embodiment 9. According to the color conversion film of Embodiment 8, the color conversion film also includes a singlet oxygen quencher.

Embodiment 10. According to the color conversion film of Embodiment 8, the color conversion film also includes a radical scavenger.

Embodiment 11. The color conversion film according to embodiment 8, wherein the thickness of the film is between 10 μm and about 200 μm.

Embodiment 12. The color conversion film of embodiment 8, wherein the film absorbs blue light in the wavelength range of 400 nm to 480 nm, and emits red light in the wavelength range of 575 nm to 645 nm.

Embodiment 13. The color conversion film according to Embodiment 8, the color conversion film also includes a photoluminescence composite having an absorbance of 400 nm to 480 nm light wavelength and an emission of 510 nm to 560 nm light wavelength.

Embodiment 14. A method for preparing the color conversion film according to Embodiments 8, 9, 10, 11, 12, and 13, the above method comprising: dissolving a resin matrix and at least one photoluminescent compound in a solvent, wherein The aforementioned at least one photoluminescent composite is described in Embodiments 1, 2, 3, 4, 5, 6, and 7; and the aforementioned mixture is applied to the surface of the aforementioned transparent substrate.

Embodiment 15. According to the method of Embodiment 14, the above method also includes dissolving the photoluminescent complex having an absorbance in the range of 400 nm to 480 nm and emission in the wavelength range of 510 nm to 560 nm.

Embodiment 16. According to the method of Embodiment 14, the above method also includes dissolving the radical scavenger in the above solvent.

Embodiment 17. According to the method of Embodiment 14, the above method also includes dissolving the singlet oxygen quencher in the above solvent.

Embodiment 18. A backlight unit including the color conversion film according to Embodiment 8.

Embodiment 19. A display device including the backlight unit according to Embodiment 18.

Examples The following are examples of methods for preparing and using the photoluminescent composites described herein.

CE-1 ： 將0.75 g之4-羥基-2,6-二甲基苯甲醛(5 mmol)及1.04 g之2,4-二甲基吡咯(11 mmol)溶於100 mL之無水二氯甲烷中。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。第二天將溶液過濾，然後用二氯甲烷洗滌，得到二吡咯甲烷。接下來，將1.0 g之二吡咯甲烷溶於60 mL之TNF中。將5 mL之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，並藉由使用二氯甲烷作為溶離劑之快速層析法純化。收集所需級分，並減壓乾燥，得到0.9 g之橙色固體(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. The next day, the solution was filtered and then washed with dichloromethane to obtain dipyrromethene. Next, 1.0 g of dipyrromethene was dissolved in 60 mL of TNF. 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) : It was synthesized as described in Wakamiya, Atsushi et al., Chemistry Letters, 37(10), 1094-1095; 2008

Example 2. Synthesis of photoluminescent composite: Example 2.1 : RLE-1

Compound 1 (4,5 -dihydro- 1H- benzo [g] indole ) : a mixture of DMSO (50 mL), KOH (3.36 g) and NH2OH.HCl (4.17 g) was stirred at room temperature for 30 minutes , Then add 1-tetralone (7.3 g) in DMSO (25ml). The mixture was stirred at 70°C for 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. Use dichloromethane/hexane (0%→30%) eluent to perform flash chromatography (silica gel) on the solution, and collect the second main fraction. After removing the solvent under reduced pressure, a pale yellow solid was obtained as the desired product (3.5 g, yield 41%). LCMS (APCI+): _{calculated value for C 12} H ₁₂ N (M+H): 170; found value: 170.

Compound 1.1 (4-( bis (4,5 -dihydro- 1H- benzo (g) indol- 2- yl ) methyl )-3,5 -dimethylphenol ): 4,5-dihydro -1H-benzo[g]indole (0.34 g, 2 mmol), 4-hydroxy-2,5-dimethylbenzaldehyde (0.15 g, 1 mmol) and a drop of trifluoroacetic acid in 1,2-dichloro The mixture in ethane (20 mL) was degassed for 10 minutes and then stirred at 30°C for 20 hours. After cooling to room temperature, the mixture was filtered, and the solid was collected as the desired product (0.2 g, yield 43%). LCMS (APCI+): _{Calculated value of C 33} H ₃₁ N ₂ O (M+H): 471; actually measured value: 471.

Compound 1.2 : To a solution of compound 1.1 (200 mg, 0.42 mmol) in 20 mL of dichloromethane was added tetrachloro-p-benzoquinone (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 -ether. The whole was stirred overnight at room temperature, then loaded onto 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 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.

Compound 1.3 (5 -oxo -5-( perylene- 3 -yl ) valeric acid ) : Add a stir bar to a 3L 2-neck round-bottomed flask, and rinse thoroughly with argon. AlCl ₃ (34.7 mmol, 4.624 g) was added to the flask, and then anhydrous dichloromethane (600 mL) was added. The reaction mixture was cooled to 0°C with an ice-water bath, and methyl 5-chloro-5-oxovalerate (30.4 mmol, 5.00 g) was added via a syringe under argon stirring. The mixture was stirred at 0°C for 1 hour, and then perylene (28.9 mmol, 7.300 g) was added with stirring. The cooling bath was removed, and the reaction mixture was stirred at room temperature for 2 hours. The flask was equipped with a finned air condenser and heated in a heating block set at 45°C while stirring under argon overnight. The reaction mixture was cooled to room temperature and quenched by adding crushed ice (600 mL, loosely packed). To this mixture was added 6N aqueous HCl (100 mL). Continue stirring until all the ice has melted. The layers were separated, and the aqueous layer was extracted with DCM (2×200 mL). The combined organic layers were dried over MgSO _4, filtered, and concentrated in vacuo. The crude reaction was purified by silica gel flash chromatography (100% DCM (3 CV)→5% EtOAc/DCM (10 CV)). The product-containing fractions were collected and concentrated in vacuo to obtain 3.810 g, 35% yield. MS (APCI): _{Calculated value of C 26} H ₂₀ O ₃ (M+H)=381; actually measured value: 381.

Next, add a stir bar to a 250 mL 2-neck round bottom flask and flush with argon. Into the flask were added methyl 5-oxo-5-(perylene-3-yl)valerate (3.00 mmol, 1.141 g) and KOH (30.0 mmol, 1.683 g), and then ethanol (200 standard Alcohol content, 200 mL). The flask was equipped with a finned air condenser and heated in a heating block at 95°C for two hours under argon with stirring. The reaction mixture was cooled to room temperature and diluted with water in an Erlenmeyer flask (to a total volume of 500 mL) and quenched with 6N aqueous HCl (5 mL). The resulting precipitate was collected and concentrated in vacuo to obtain 1.013 g (92% yield). MS (APCI): _{Calculated value of C 25} H ₁₈ O ₃ (MH)=365, measured value: 365.

RLE-1 : To compound 1.2 (52 mg, 0.1 mmol), perylene compound 1.3 [5-oxo-5-9-perylene-3-yl]valeric acid (48 mg, 0.13 mmol) , DMAP (25 mg, 0.2 mmol), p-TsOH (34 mg, 0.18 mmol) in dichloromethane (7 mL), add DIC (63 mg, 0.5 mmol) in 1 mL of dichloromethane . The whole was stirred overnight at room temperature, and then purified by flash chromatography (silica gel) using dichloromethane/hexane (0%→80%) eluent. The required fractions were collected, and after removing the solvent, a dark green solid (70 mg, 81% yield) was obtained. LCMS (APCI+): _{calculated value of C 58} H ₄₄ BF ₂ N ₂ O ₃ (M+H): 865; found value: 865. ¹ H NMR (400 MHz, dichloromethane- d ₂ ) δ 8.66 (d, J = 8.0 Hz, 2H), 8.50 (d, J = 8.6 Hz, 1H), 8.25-8.16 (m, 4H), 7.89 ( d, J = 8.0 Hz, 1H), 7.69 (dd, J = 17.5, 8.1 Hz, 2H), 7.54 (dd, J = 8.6, 7.6 Hz, 1H), 7.46 (td, J = 7.8, 2.5 Hz, 2H ), 7.36 (td, J = 7.6, 1.7 Hz, 2H), 7.27-7.18 (m, 4H), 6.86 (s, 2H), 6.27 (s, 2H), 3.17 (t, J = 7.1 Hz, 2H) , 2.83 (dd, J = 8.3, 5.9 Hz, 4H), 2.70 (t, J = 7.3 Hz, 2H), 2.57 (dd, J = 8.3, 5.8 Hz, 4H), 2.20 (q, J = 7.2 Hz, 2H), 2.14 (s, 6H).

RLE-2 ：向化合物1.2 (52 mg，0.1 mmol)、4-(二萘嵌苯-3-基)丁酸(44 mg，0.13 mmol)、DMAP (25 mg，0.2 mmol)、p-TsOH (34 mg，0.18 mmol)在二氯甲烷(7 mL)中之溶液中加入DIC (63 mg，0.5 mmol)在1 mL二氯甲烷中之溶液。整體在室溫下攪拌隔夜，然後藉由使用二氯甲烷/己烷(0%à70%)溶離劑進行快速層析法(矽膠)來純化。收集所需級分，在移除溶劑後，獲得了深綠色固體(80 mg，產率為95.6%)。LCMS (APCI+)：C₅₇ H₄₄ BF₂ N₂ O₂ (M+H)之計算值：837；實測值：837。¹ H NMR (400 MHz, 二氯甲烷-d ₂ ) δ 8.79 (d,J = 8.0 Hz, 2H), 8.34-8.20 (m, 4H), 8.04 (d,J = 8.4 Hz, 1H), 7.74 (dd,J = 8.2, 4.9 Hz, 2H), 7.66-7.45 (m, 6H), 7.40 (dd,J = 7.4, 1.2 Hz, 1H), 7.38-7.31 (m, 3H), 6.94 (s, 2H), 6.39 (s, 2H), 3.24 (dd,J = 8.6, 6.7 Hz, 2H), 2.96 (dd,J = 8.3, 5.9 Hz, 4H), 2.78 (t,J = 7.2 Hz, 2H), 2.70 (dd,J = 8.3, 5.9 Hz, 4H), 2.30 (dt,J = 9.1, 7.2 Hz, 2H), 2.24 (s, 6H)。 Example 2.2 RLE 2 :

RLE-2 : To compound 1.2 (52 mg, 0.1 mmol), 4-(perylene-3-yl)butyric acid (44 mg, 0.13 mmol), DMAP (25 mg, 0.2 mmol), p-TsOH ( A solution of 34 mg, 0.18 mmol) in dichloromethane (7 mL) was added to a solution of DIC (63 mg, 0.5 mmol) in 1 mL dichloromethane. The whole was stirred overnight at room temperature, and then purified by flash chromatography (silica gel) using dichloromethane/hexane (0%→70%) eluent. The required fractions were collected and after removing the solvent, a dark green solid was obtained (80 mg, 95.6% yield). LCMS (APCI+): _{calculated value of C 57} H ₄₄ BF ₂ N ₂ O ₂ (M+H): 837; actually measured value: 837. ¹ H NMR (400 MHz, dichloromethane- d ₂ ) δ 8.79 (d, J = 8.0 Hz, 2H), 8.34-8.20 (m, 4H), 8.04 (d, J = 8.4 Hz, 1H), 7.74 ( dd, J = 8.2, 4.9 Hz, 2H), 7.66-7.45 (m, 6H), 7.40 (dd, J = 7.4, 1.2 Hz, 1H), 7.38-7.31 (m, 3H), 6.94 (s, 2H) , 6.39 (s, 2H), 3.24 (dd, J = 8.6, 6.7 Hz, 2H), 2.96 (dd, J = 8.3, 5.9 Hz, 4H), 2.78 (t, J = 7.2 Hz, 2H), 2.70 ( dd, J = 8.3, 5.9 Hz, 4H), 2.30 (dt, J = 9.1, 7.2 Hz, 2H), 2.24 (s, 6H).

化合物 3.1 (8- 溴 -4,5- 二氫 -1H- 苯并 [g] 吲哚 ) ： 一個250 mL之2頸圓底燒瓶裝有帶翅片之冷凝器、攪拌棒及氣體連接管。用氬氣沖洗燒瓶，並將KOH (85%之純度，60.0 mmol，4.106 g)及NH₂ OH.HCl (60.0 mmol，4.169 g)加入至該燒瓶中，之後立即加入無水DMSO (5 mL)。將該混合物在室溫下在氬氣下攪拌5分鐘，然後加入7-溴-3,4-二氫萘-1(2H)-酮(50.0 mmol，11.255 g)。將燒瓶塞住並且在室溫下攪拌1分鐘，然後在加熱塊中加熱至110℃持續1小時。向燒瓶中加入更多KOH (85%之純度，300 mmol，16.833 g)，並將加熱塊之溫度升至140℃。將無水二氯乙烷(200 mmol，15.8 mL)用無水DMSO稀釋至40 mL之總體積。將該溶液轉移至50 mL注射器中，並在30分鐘之時段內在140℃下在非常劇烈之攪拌下加入至反應混合物中。製備更多的二氯乙烷/DMSO溶液，並在附加30分鐘內藉由注射器泵加入附加10 mL之該混合物。將該反應混合物在冰水浴中冷卻至0℃，並用飽和含水氯化銨(100 mL)進行猝滅。將該混合物用水(400 mL)稀釋，並用乙醚(250 mL)及乙酸乙酯(100 mL)萃取。將該2相混合物在室溫下劇烈攪拌，然後濾過矽藻土墊以移除固體。用醚(2×200 mL)萃取水層。將合併之有機層用水(5×50 mL)、鹽水(50 mL)洗滌，經MgSO₄ 乾燥，過濾，並蒸發至乾燥。將粗製混合物藉由在矽膠(100%之己烷(1 CV)à10%之DCM/己烷(1 CV)à30%之DCM/己烷(9 CV))上進行快速層析法而純化。在矽膠(100%之己烷(1 CV)à1%之乙酸乙酯/己烷(0 CV)à10%之乙酸乙酯/己烷(9 CV))上重新純化產物級分。將產物級分收集並旋轉蒸發，得到4.507 g，產率為36%。主要雜質包括N-乙烯基產物及兩個O-鍵合之乙烯橋接肟。MS (APCI)：C₁₂ H₁₀ BrN (M + H)之計算值=248；實測值：248。 Example 2.3 RLE-3 :

Compound 3.1 (8- Bromo -4,5 -dihydro- 1H- benzo [g] indole ) : A 250 mL 2-neck round-bottom flask is equipped with a finned condenser, stir bar and gas connection tube. The flask was flushed with argon, and KOH (85% purity, 60.0 mmol, 4.106 g) and NH ₂ OH.HCl (60.0 mmol, 4.169 g) were added to the flask, and then anhydrous DMSO (5 mL) was immediately added. The mixture was stirred at room temperature under argon for 5 minutes, and then 7-bromo-3,4-dihydronaphthalene-1(2H)-one (50.0 mmol, 11.255 g) was added. The flask was stoppered and stirred at room temperature for 1 minute, then heated to 110°C in a heating block for 1 hour. Add more KOH (85% purity, 300 mmol, 16.833 g) to the flask, and increase the temperature of the heating block to 140°C. Dilute anhydrous dichloroethane (200 mmol, 15.8 mL) with anhydrous DMSO to a total volume of 40 mL. The solution was transferred to a 50 mL syringe and added to the reaction mixture at 140°C under very vigorous stirring over a period of 30 minutes. Prepare more dichloroethane/DMSO solution and add an additional 10 mL of this mixture via a syringe pump within an additional 30 minutes. The reaction mixture was cooled to 0°C in an ice water bath and quenched with saturated aqueous ammonium chloride (100 mL). The mixture was diluted with water (400 mL) and extracted with ether (250 mL) and ethyl acetate (100 mL). The 2-phase mixture was stirred vigorously at room temperature and then filtered through a pad of Celite to remove solids. The aqueous layer was extracted with ether (2×200 mL). The combined organic layer was washed with water (5×50 mL), brine (50 mL), dried over MgSO ₄ , filtered, and evaporated to dryness. The crude mixture was purified by flash chromatography on silica gel (100% hexane (1 CV)→10% DCM/hexane (1 CV)→30% DCM/hexane (9 CV)). The product fraction was repurified on silica gel (100% hexane (1 CV) à 1% ethyl acetate/hexane (0 CV) à 10% ethyl acetate/hexane (9 CV)). The product fractions were collected and rotary evaporated to obtain 4.507 g with a yield of 36%. The main impurities include N-vinyl products and two O-bonded ethylene bridged oximes. MS (APCI): _{calculated value of C 12} H ₁₀ BrN (M + H)=248; measured value: 248.

Compound 3.2 ((T-4)-[2-(4,5 -Dihydro- 8- bromo -2H- benzo [g] indol- 2- ylidene- κ N )-(3,5 -dimethyl -4-hydroxyphenyl) methyl] -4,5-dihydro -1H- benzo [g] indol-sulfato -κ N] boron difluoride): 250 mL of a 2 neck round bottom flask There are gas connecting pipes and stirring rods. The flask was flushed with argon, and compound 3.1 (5.21 mmol, 1.293 g) and 4-hydroxy-2,6-dimethylbenzaldehyde (2.66 mmol, 399 mg) were added to the flask, and then anhydrous dichloroethane was added Alkane (50 mL). The reaction mixture was bubbled with argon for 30 minutes, and then TFA (0.1% v/v, 50 μL) was added via a syringe. The reaction mixture was bubbled with argon for another 15 minutes, and then the reaction mixture was stirred at room temperature under argon for 1 hour. A finned condenser was added to the reaction flask, and the reaction was heated and stirred in a heat block at 50°C for 24 hours. The reaction was cooled to 0°C in an ice water bath, and p-tetrachlorobenzoquinone (2.61 mmol, 641 mg) was added with stirring. The reaction was stirred at 0°C for 20 minutes, at which time the oxidation was complete. _{BF 3} .OEt ₂ (58.4 mmol, 7.2 mL) and triethylamine (34.9 mmol, 4.9 mL) were added to the reaction, and the mixture was stirred at 0°C for 30 minutes, then the ice-water bath was removed and the reaction was heated Stir at room temperature for three days. The reaction was then heated to 60°C in a heating block for 6 hours. Evaporate the reaction mixture to dryness and apply it to silica gel (100% hexane (1 CV) à 10% ethyl acetate/hexane (0 CV) à 50% ethyl acetate/hexane (8 CV) à 60% acetic acid Ethyl acetate/hexane (0 CV)→60% ethyl acetate/hexane (2 CV)) was purified by flash chromatography. Most of the product lysates are pure, and some co-lysates contain impurities. Collect the impure fraction, evaporate, and apply it to silica gel (100% hexane (2 CV) à 20% ethyl acetate/hexane (0 CV) à 50% ethyl acetate/hexane (10 CV) ) Was purified again by flash chromatography. The pure fractions from the two columns were combined and evaporated to dryness to give 1170 mg of product with a yield of 67%. MS (APCI): _{Calculated value of C 33} H ₂₅ BBr ₂ F ₂ N ₂ O (M ^- )=672; actually measured value: 672. ¹ H NMR (400 MHz, chloroform-d) δ 9.01 (d, J = 2.0 Hz, 2H), 7.43 (dd, J = 8.1, 2.0 Hz, 2H), 7.12 (d, J = 8.1 Hz, 2H), 6.63 (s, 2H), 6.34 (s, 2H), 2.85 (dd, J = 8.3, 5.9 Hz, 4H), 2.65 (dd, J = 8.4, 5.8 Hz, 4H), 2.17 (s, 6H).

RLE-3 ((T-4)-[2-[(4,5 -Dihydro- 8- bromo -2H- benzo [g] indol- 2- ylidene- κ N )-(3,5- Dimethyl- 4-( perylene- 3 -yl ) butyrate ) phenyl ) methyl ]-4,5 -dihydro- 1H- benzo [g] indolato- κ N ] two Boron fluoride ) : Synthesis using compound 3.2 (0.100 mmol, 67 mg) and 4-(perylene-3-yl)butyric acid (0.150 mmol, 51 mg) in a similar manner to RLE-2 at room temperature RLE-3 overnight. The compound was purified by flash chromatography on silica gel (100% DCM (1 CV)→10% ethyl acetate/DCM (10 CV)). The product fractions were collected and evaporated to dryness to obtain 95 mg with a yield of 95%. MS (APCI): _{Calculated value of C 57} H ₄₁ BBr ₂ F ₂ N ₂ O ₂ (M ^- )=992; actually measured value: 992. ¹ H NMR (400 MHz, chloroform-d) δ 9.01 (d, J = 1.3 Hz, 1H), 8.27-8.15 (m, 4H), 7.97 (d, J = 8.4 Hz, 1H), 7.68 (dd, J = 8.1, 4.7 Hz, 2H), 7.56 (t, J = 8.0 Hz, 1H), 7.48 (td, J = 7.8, 1.7 Hz, 2H), 7.46-7.39 (m, 3H), 7.12 (d, J = 8.1 Hz, 2H), 6.87 (s, 2H), 6.33 (s, 2H), 3.21 (t, J = 7.6 Hz, 2H), 2.85 (t, J = 7.1 Hz, 3H), 2.74 (t, J = 7.1 Hz, 2H), 2.65 (t, J = 7.1 Hz, 2H), 2.27 (p, J = 7.2 Hz, 2H), 2.19 (s, 6H).

Example 2.4 RLE-4 :

Compound 4.1 (3-methyl-4,5-dihydro-1H-benzo[g]indole-2-carboxylic acid tertiary butyl ester): Step 1: Under ice-cooling Slowly add NaNO2 (4.5 g) to a solution of tertiary butyl acid (10 mL) in 20 mL HOAc, while keeping the temperature of the reaction mixture between 5-10°C. After the addition, the whole was stirred at room temperature for one hour, and then 20 mL of HOAc was added, and the resulting oxime solution was used in step 2 without further purification. Step 2: Dissolve 1-tetralone (8.8 g) together with 10 g NaOAc in 100 mL HOAc, and heat the mixture to 100°C. The oxime solution from step 1 was added dropwise to the mixture while slowly adding zinc powder. After adding both oxime and zinc, the whole was heated at 110°C for one hour, then cooled to 70°C, and poured into ice water (1.8 L). The mixture was allowed to stand overnight, and then the solid was collected by filtration, and the solid was purified by flash chromatography (silica gel) using dichloromethane/hexane (0%→40%) eluent. The fourth fraction was collected and the solvent was removed to obtain the desired product (0.15 g, yield 1%) as a white solid. LCMS (APCI+): _{calculated value for C 18} H ₂₂ NO ₂ (M+H): 284; found value: 284.

Compound 4.2 : To a solution of compound 4.1 (150 mg, 0.53 mmol) in dichloroethane (5 mL) was added 1 mL of trifluoroacetic acid. The solution was degassed for 10 minutes and then stirred at room temperature for one hour. To the resulting solution was added 4-hydroxybenzaldehyde (30 mg), and the solution was stirred overnight to form dipyrrole-methane. After removing the solvent under reduced pressure, 6 mL of dichloroethane was added to dissolve the resultant product. Tetrachloro-p-benzoquinone (65 mg) was added to the solution under cooling in an ice water bath and stirred for one hour. Then BF ₃ -ether (0.5 mL) and trimethylamine (0.5 mL) were added, and the mixture was stirred at room temperature overnight, then treated with 1N HCl (50 mL) and extracted with dichloromethane. The organic phase was collected, dried over MgSO ₄ , loaded onto silica gel, and purified by flash chromatography using dichloromethane/hexane (0%→80%) eluent. Collect the required red luminescent fractions and remove the solvent to obtain the desired product as a solid (6 mg, yield 5%). LCMS (APCI+): _{calculated value of C 33} H ₂₈ BF ₂ N ₂ O (M+H): 517; found value: 517.

RLE-4 : To compound 4.2 (6 mg, 0.012 mmol), 4-(perylene-3-yl)butyric acid (6 mg, 0.015 mmol), DMAP/p-TsOH salt (6 mg, 0.02 mmol) Add a solution of DIC (10 mg) in 1 mL of dichloromethane to a solution of the mixture in dichloromethane (3 mL). The mixture was stirred at room temperature overnight, then loaded onto silica gel, and purified by flash chromatography using dichloromethane/hexane (0%→50%) eluent. The required red luminescent fraction was collected, and after the solvent was removed, the desired product (3 mg, 33% yield) was obtained as a dark green solid. LCMS (APCI+): _{calculated value of C 57} H ₄₄ BF ₂ N ₂ O ₂ (M+H): 836; actually measured value: 836. ¹ H NMR (400 MHz, dichloromethane- d ₂ ) δ 8.73 (d, J = 8.0 Hz, 2H), 8.30-8.16 (m, 4H), 8.00 (dd, J = 8.4, 1.0 Hz, 2H), 7.70 (dd, J = 8.1, 4.9 Hz, 2H), 7.62-7.37 (m, 8H), 7.37-7.24 (m, 6H), 3.25-3.17 (m, 2H), 2.89 (t, J = 7.0 Hz, 4H), 2.76 (t, J = 7.2 Hz, 2H), 2.55 (t, J = 7.1 Hz, 4H), 2.32-2.20 (m, 2H), 1.40 (s, 6H).

化合物 5.1 (1-(2- 溴苯基 ) 環戊 -1- 醇 ) ： 烘乾之250 mL 2頸圓底燒瓶裝有氣體連接管及攪拌棒，並用氬氣沖洗。將該燒瓶用隔膜密封，並經由注射器裝填鎂屑(145 mmol，3.525 g)及無水THF (100 mL)。烘乾之100 mL 2頸圓底燒瓶裝有氣體連接管，並用氬氣沖洗。將該燒瓶用隔膜密封，並裝填無水THF (60 mL)。向該100 mL燒瓶中加入1,5-二溴戊烷(70.0 mmol，8.30 mL)。將250 mL之燒瓶在0℃之冰水浴中冷卻，並在劇烈攪拌下經由注射器加入1,5-二溴戊烷溶液持續5分鐘。將冰水浴移除並用室溫水浴替代，並將反應混合物在室溫下攪拌。當在室溫下攪拌4小時時，反應變得略微混濁。一個1000 mL 2頸圓底燒瓶裝有氣體連接管及攪拌棒，並用氬氣沖洗。將第二頸部用隔膜密封，並加入無水THF (60 mL)。在室溫攪拌下向該燒瓶中加入2-溴苯甲酸乙酯(50.0 mmol，7.94 mL)。將該燒瓶在冰水浴中冷卻至0℃，並在劇烈攪拌下經由套管加入雙格氏試劑溶液持續約5分鐘。將反應混合物在0℃攪拌15分鐘，然後在室溫下攪拌3小時。將反應混合物冷卻至0℃並用飽和氯化銨溶液(50 mL)猝滅。將反應混合物進一步用水(500 mL)稀釋，並用乙酸乙酯(3×150 mL)萃取。將合併之有機層用鹽水(150 mL)洗滌，經MgSO₄ 乾燥，過濾，並藉由旋轉蒸發而濃縮成淡黃色油狀物。此種油狀物純至足以用於下一步驟。得到11.145g (92%之產率)。MS (APCI)：C₁₁ H₁₃ BrO (M+H)之計算值=241；實測值：241。 Example 2.5 RLE-5

Compound 5.1 (1-(2- bromophenyl ) cyclopentan- 1- ol ) : A 250 mL 2-neck round-bottomed flask, which was dried, was equipped with a gas connection tube and a stirring rod, 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 filled via a syringe. The oven-dried 100 mL 2-neck round bottom flask is equipped with a gas connection tube and flushed with argon. The flask was sealed with a septum and filled with anhydrous THF (60 mL). To the 100 mL flask was added 1,5-dibromopentane (70.0 mmol, 8.30 mL). The 250 mL flask was cooled in an ice-water bath at 0°C, and the 1,5-dibromopentane solution was added via a syringe with vigorous stirring for 5 minutes. The ice water bath was removed and replaced with a room temperature water bath, and the reaction mixture was stirred at room temperature. When stirred at room temperature for 4 hours, the reaction became slightly turbid. A 1000 mL 2-neck round bottom flask is equipped with a gas connection tube and a stirring rod, and is flushed with argon. The second neck was sealed with a septum, and anhydrous 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 cannula under vigorous stirring for 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 layer was washed with brine (150 mL), dried over MgSO ₄ , filtered, and concentrated by rotary evaporation to a pale yellow oil. This oil is pure enough to be used in the next step. Obtained 11.145 g (92% yield). MS (APCI): _{calculated value of C 11} H ₁₃ BrO (M+H)=241; measured value: 241.

Compound 5.2 (3-(1-(2- bromophenyl ) cyclopentyl )-1 -tosyl- 1H- pyrrole /2-(1-(2- bromophenyl ) cyclopentyl )-1- Tosyl- 1H- pyrrole ) : Add a stir bar to a 250 mL 2-neck round bottom flask and assemble a gas connection tube. 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 on silica gel (100% hexane (1 CV) à 15% EtOAc/hexane (10 CV)). 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.

Compound 5.3 (2-(1-(2- bromophenyl ) cyclopentyl )-1 -tosyl- 1H- pyrrole ) : A 40 mL screw cap vial was filled with a stir bar. To this vial was added the mixture from compound 2.2 (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. The oxygen in the vial is purged by vacuum/backfill argon cycle (3 times). The reaction mixture was stirred overnight under argon in a heating block at 110°C. 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. Purified by flash chromatography on silica gel (10% DCM/hexane (1 CV)→50% DCM/hexane (10 CV)). 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.

Compound 5.4 (1'H- spiro [ cyclopentane -1,4'- indeno [1,2-b] pyrrole ) : Add a stir bar to a 100 mL 2-neck round-bottomed flask, and assemble fins to condense Device and gas connection pipe. The flask was flushed with argon and the mixture from compound 2.3 (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 and the residue was dispersed into saturated ammonium chloride (25 mL) and water (100 mL). The product was filtered off, dried, and purified by flash chromatography on silica gel (100% hexane (1 CV) à 20% EtOAc/hexane (10 CV)). The product-containing fraction was dried by rotary evaporation to obtain 279 mg (yield 74%) 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 5.5 (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] diazaborane- 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 connection tube. The flask was flushed with argon, and compound 2.4 (1.31 mmol, 275 mg) and 4-hydroxy-2,6-dimethylbenzaldehyde (0.683 mmol, 103 mg) were added, 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 μL) 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. _{BF 3} .OEt ₂ (14.67 mmol, 1.8 mL) and triethylamine (8.78 mmol, 1.2 mL) were added to the reaction, and the mixture was stirred at 0° C. and slowly warmed to room temperature for 4 hours. The water bath was removed and replaced by 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 on silica gel (100% DCM (4 CV)→5% EtOAc/DCM (5 CV)→5% EtOAc/DCM). The column is eluted until the tail product has been eluted. Obtained 314 mg, the yield was 85%. MS (APCI): _{The calculated value of C 39} H ₃₅ BF ₂ N ₂ O (M ^- )=596; the measured value is 596.

RLE-5 : (4-(6',6' -Difluoro -6'H- 5'l4,6'l4-Dispiro [ 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 -dimethylphenyl 4-( perylene- 3 -yl ) butyrate ) : in a 40 mL screw cap vial Add a stir bar, compound 2.5 (0.100 mmol, 60 mg), 4-(perylene-3-yl)butyric acid (0.150 mmol, 51 mg) and DMAP:pTsOH 1:1 salt (0.200 mmol, 59 mg) . Rinse the vial with argon, and add anhydrous dichloromethane (20 mL). 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 ultrasonicated for 30 seconds. An additional portion of 4-(perylene-3-yl)butyric acid (0.150 mmol, 51 mg) was added and stirred at 50°C overnight under argon. The solvent was evaporated and the product was purified by flash chromatography on silica gel (100% hexane (1 CV)→5% EtOAc/hexane (0 CV)→40% EtOAc/hexane (10 CV)). The product fraction was evaporated and purified for the second time (100% hexane (1 CV)→10% ethyl acetate/hexane (0 CV)→30% ethyl acetate/hexane (10 CV)). The fractions containing pure product were evaporated to obtain 42 mg (52% yield). MS (APCI): _{Calculated value of C 63} H ₅₁ BF ₂ N ₂ O ₂ (M ^- )=915; measured value: 915.

化合物 6.1 (1,4,5,6-四氫苯并[6,7]環庚烷[1,2-b]吡咯)：將KOH (1.35 g)、NH₂ OH.HCl (1.67 g)在10 mL DMSO中之混合物脫氣，並在室溫下攪拌30分鐘。向該混合物中加入1-苯并環庚酮(3.2 g)在10 mL DMSO中之溶液。將所得混合物在70℃下攪拌30分鐘。然後加入KOH (2.0 g)，並將混合物加熱至140℃，並在一個小時內滴加1,2-二氯乙烷(2.38 g)在DMSO (10 mL)中之溶液。在冷卻至室溫後，將溶液倒入飽和NH₄ Cl溶液(100 mL)中。將溶液用乙酸乙酯(100 mL×3)萃取。將有機相經Na₂ SO₄ 乾燥，加載至矽膠上，並藉由使用二氯甲烷/己烷(0%à30%)溶離劑進行快速層析法而純化。將第二主級分收集作為所需產物，在移除溶劑後，獲得了白色固體(0.22 g，產率為8.5%)。LCMS (APCI+)：C₁₃ H₁₄ N (M+H)之計算值：184；實測值：184。 Example 2.6 : RLE-6

Compound 6.1 (1,4,5,6-tetrahydrobenzo[6,7]cycloheptane[1,2-b]pyrrole): _{Combine KOH (1.35 g), NH 2} OH.HCl (1.67 g) in The mixture in 10 mL DMSO was degassed and stirred at room temperature for 30 minutes. To this mixture was added a solution of 1-benzocycloheptanone (3.2 g) in 10 mL DMSO. The resulting mixture was stirred at 70°C for 30 minutes. Then KOH (2.0 g) was added, and the mixture was heated to 140°C, and a solution of 1,2-dichloroethane (2.38 g) in DMSO (10 mL) was added dropwise within one hour. After cooling to room temperature, the solution was poured into saturated NH ₄ Cl solution (100 mL). The solution was extracted with ethyl acetate (100 mL×3). The organic phase was _{dried over Na 2} SO ₄ , loaded onto silica gel, and purified by flash chromatography using dichloromethane/hexane (0%→30%) eluent. The second main fraction was collected as the desired product, after removing the solvent, a white solid was obtained (0.22 g, yield 8.5%). LCMS (APCI+): _{calculated value for C 13} H ₁₄ N (M+H): 184; found value: 184.

Compound 6.2 : Degas a mixture of compound 8 (0.22 g, 1.2 mmol), 4-hydroxy-2,5-dimethylbenzaldehyde (0.09 ng, 0.6 mmol) and a drop of TFA in dichloroethane for 30 minutes, It was then heated at 40°C overnight. After cooling to room temperature, it was cooled with an ice water bath, tetrachloro-p-benzoquinone (0.2 g) was added, and the mixture was stirred for 20 minutes. Then BF ₃ -ether (0.8 mL) and trimethylamine (0.5 mL) were added. The mixture was heated at 50°C for two hours, then loaded onto silica gel and purified by flash chromatography using dichloromethane/hexane (10%→90%) eluent. After removing the solvent, the desired product (54 mg, yield 16%) was obtained. LCMS (APCI1): _{Calculated value of C 35} H ₃₀ BF ₂ N ₂ O (MH): 543; actually measured value: 543.

RLE-6 : To compound 9 (54 mg, 0.1 mmol), 4-(perylene-3-yl)butyric acid compound 5 (50 mg, 0.15 mmol), DMAP/p-TsOH salt (60 mg, 0.2 mmol) Add a solution of DIC (60 mg, 0.5 mmol) in 1 mL of dichloromethane to the mixture in 7 mL of dichloromethane. The mixture was stirred at room temperature overnight, then loaded onto silica gel and purified by flash chromatography using dichloromethane/hexane (10%→70%) eluent. The required fractions were collected and the solvent was removed to obtain a solid (75 mg, 87% yield). LCMS (APCI-): _{Calculated value of C 59} H ₄₇ BF ₂ N ₂ O ₂ (M-): 864; actually measured value: 864. ¹ H NMR (400 MHz, methylene chloride- d ₂ ) δ 8.35-8.21 (m, 4H), 8.05 (d, J = 8.7 Hz, 2H), 7.74 (dd, J = 8.1, 5.0 Hz, 2H) , 7.67-7.59 (m, 1H), 7.59-7.46 (m, 3H), 7.38 (td, J = 6.0, 5.5, 3.5 Hz, 4H), 7.33 (q, J = 5.1, 4.4 Hz, 2H), 6.96 (s, 2H), 6.47 (s, 2H), 5.37 (s, 15H), 3.29-3.21 (m, 2H), 2.79 (t, J = 7.2 Hz, 2H), 2.66 (t, J = 6.8 Hz, 4H), 2.32 (d, J = 7.3 Hz, 3H), 2.29 (s, 6H), 2.07 (p, J = 7.0 Hz, 4H).

化合物 7.1 ：(3-甲基-1,4,5,6-四氫苯并[6,7]環庚烷[1,2-b]吡咯-2-羧酸三級丁酯)：步驟1.將3-側氧基丁酸三級丁酯(10 mL)溶於乙酸(20 mL)中，並將該溶液用冰浴冷卻。向該溶液中成批加入亞硝酸鈉(4.5 g)，與此同時將該混合物保持在10℃下。在一個小時後，移除冰浴，並使混合物加溫至室溫，並攪拌一個小時以形成肟溶液。 Example 2.7 RLE-7

Compound 7.1 : (3-methyl-1,4,5,6-tetrahydrobenzo[6,7]cycloheptane[1,2-b]pyrrole-2-carboxylic acid tertiary butyl ester): Step 1 . Dissolve tertiary butyl 3-oxobutyrate (10 mL) in acetic acid (20 mL), and cool the solution with an ice bath. To this solution was added sodium nitrite (4.5 g) in batches while maintaining the mixture at 10°C. After one hour, the ice bath was removed, and the mixture was warmed to room temperature and stirred for one hour to form an oxime solution.

Step 2. Add a solution of 1-benzocycloheptanone (3.2 g) in 25 mL of acetic acid to the solution prepared above, and then add zinc powder (11.25 g) in batches. The resulting mixture was stirred at 75°C for one hour, and then the mixture was cooled to room temperature, and then 10 mL of water was added and left to stand for one hour. The solid was filtered off, and the filtrate was poured into 100 mL of water and left to stand overnight. The resulting solid was collected by filtration, re-dissolved in dichloromethane and loaded on silica gel for purification by flash chromatography using dichloromethane/hexane (0%→90%) eluent. The desired product was collected as the second fraction. After removing the solvent, a white solid (0.15 g, 2.5% yield) was obtained. LCMS (APCI+): _{calculated value for C 19} H ₂₄ NO ₂ (M+H): 298; found value: 298.

Compound 7.2 : Compound 7.1 (50 mg, 0.168 mmol) was dissolved in 1.5 mL of TFA. The solution was degassed for 10 minutes while stirring. LCMS showed that all compound 7.1 was decarboxylated to the desired pyrrole. To this mixture was added 3 mL of dichloroethane, followed by 10 mg of 4-hydroxybenzaldehyde. The mixture was degassed for 10 minutes and stirred overnight. LCMS indicated that the main product was dipyrromethene product. Tetrachloro-p-benzoquinone (20 mg, 0.084 mmol) was added to the mixture at 0°C and stirred for 10 minutes. Then 0.4 mL of BF ₃ -ether and 1 mL of trimethylamine were added, and the resulting mixture was stirred at room temperature overnight, then loaded on the silica gel, and dissolved by using dichloromethane/hexane (0%→80%) The agent is purified by flash chromatography. After removing the solvent, the desired product was obtained (5 mg, yield 12%). LCMS (APCI-): _{Calculated value of C 35} H ₃₀ BF ₂ N ₂ O (MH): 543; actually measured value: 543.

RLE-7 : Compound 7.2 (5 mg, 0.01 mmol), 4-(perylene-3-yl)butyric acid (5 mg, 0.015 mmol), DMAP/p-TsOH salt (6 mg, 0.02 mmol) A mixture of DIC (10 mg) in 2 mL of dichloromethane was stirred overnight at room temperature, then loaded on silica gel, and flash chromatography was performed by using dichloromethane/hexane (0%→35%) eluent Method to purify. The orange-red fractions were collected and the solvent was removed to obtain a solid (3 mg, yield 35%). LCMS (APCI-): _{Calculated value of C 59} H ₄₇ BF ₂ N ₂ O ₂ (M-): 864; actually measured value: 864.

4-( 二萘嵌苯 -3- 基 ) 丁酸甲酯

步驟1：在配備有磁力攪拌棒、粉末分配器漏斗之1 L雙頸燒瓶中，在冷卻冰+水浴上將二萘嵌苯(5.22 g，20.68 mmol)在無水DCM(500 mL)中之黃色懸浮混合物進行攪拌並用氬氣鼓泡15分鐘；經由注射器及針頭緩慢加入4-(4,12b-二氫二萘嵌苯-3-基)丁酸甲酯(3.425 g，22.75 mmol)。移除冷卻浴，以讓混合物在室溫下攪拌15分鐘。將混合物再次用冰+水浴冷卻；經由粉末分配器漏斗分多個小部分加入AlCl3 (3.3 g，24.74 mmol)。將所得深紫色混合物在氬氣保護下在室溫下攪拌16小時。TLC及LCMS顯示起始材料幾乎都被消耗掉了。將反應混合物用500 mL DCM稀釋，然後倒入呈冰+水之150 mL水中，將有機層分離，用MgSO₄ 乾燥，濃縮至100 mL之體積；將SiO₂ (100 g)加入THE溶液混合物中以吸收產物，然後裝載至柱(330 g)上，用1個己烷/DCM (100:0)à(0:100)溶離，得到1.25 g所需產物。將來自柱層析法之產物及來自過濾之固體產物合併，並藉由己烷:EtAco (9:1)重結晶，得到4.24 g之黃色固體，產率為56%。LCMS (APCI+)：式C₂₅ H₁₈ O₃ 之計算值；實測值：366。¹ H NMR (400 MHz, 氯仿-d ) δ 8.57 (dd,J = 8.6, 1.0 Hz, 1H), 8.30-8.17 (m, 4H), 7.97 (d,J = 8.1 Hz, 1H), 7.78 (d,J = 8.1 Hz, 1H), 7.73 (d,J = 8.1 Hz, 1H), 7.64-7.48 (m, 3H), 3.75 (s, 3H), 3.41 (t,J = 6.5 Hz, 2H), 2.86 (t,J = 6.5 Hz, 2H)。 Example 2.8 RLE-8

Methyl 4-( Perylene- 3 -yl ) butyrate

Step 1: In a 1 L double-necked flask equipped with a magnetic stir bar and a powder distributor funnel, put perylene (5.22 g, 20.68 mmol) in anhydrous DCM (500 mL) on a cooling ice + water bath to make yellow The suspension mixture was stirred and sparged with argon for 15 minutes; methyl 4-(4,12b-dihydroperylene-3-yl)butyrate (3.425 g, 22.75 mmol) was slowly added via a syringe and needle. The cooling bath was removed to allow the mixture to stir at room temperature for 15 minutes. The mixture was cooled again with an ice+water bath; AlCl3 (3.3 g, 24.74 mmol) was added in small portions via a powder dispenser funnel. The resulting deep purple mixture was stirred at room temperature for 16 hours under the protection of argon. TLC and LCMS showed that almost all the starting material was consumed. The reaction mixture was diluted with 500 mL DCM, and then poured into 150 mL of ice+water. The organic layer was separated, dried with MgSO ₄ and concentrated to a volume of 100 mL; SiO ₂ (100 g) was added to the THE solution mixture The product was absorbed, and then loaded onto the column (330 g), and eluted with 1 hexane/DCM (100:0)→(0:100) to obtain 1.25 g of the desired product. The product from the column chromatography and the solid product from the filtration were combined and recrystallized from hexane:EtAco (9:1) to obtain 4.24 g of a yellow solid with a yield of 56%. LCMS (APCI+): _{calculated value of formula C 25} H ₁₈ O ₃ ; found value: 366. ¹ H NMR (400 MHz, chloroform- d ) δ 8.57 (dd, J = 8.6, 1.0 Hz, 1H), 8.30-8.17 (m, 4H), 7.97 (d, J = 8.1 Hz, 1H), 7.78 (d , J = 8.1 Hz, 1H), 7.73 (d, J = 8.1 Hz, 1H), 7.64-7.48 (m, 3H), 3.75 (s, 3H), 3.41 (t, J = 6.5 Hz, 2H), 2.86 (t, J = 6.5 Hz, 2H).

Step 2: In 250 mL RB, stir the yellow mixture of the product of the above step (4.24 g, 11.58 mmol) in anhydrous DCM (100 mL) on a cooling ice + water bath and bubbling with argon for 15 minutes; add slowly TFA (25 mL). The cooling bath was removed to allow the mixture to stir at room temperature for 15 minutes; triethylsilane (15 mL) was added immediately. The resulting dark mixture was stirred at room temperature for 16 hours under argon protection. TLC and LCMS showed that the starting material has been consumed. The reaction mixture was diluted with 200 mL DCM and then placed on a rotary evaporator. The TFA and DCM were concentrated. The residue was re-dissolved in DCM (50 mL), and the mixture was concentrated to dryness. The dark crude product was loaded on a SiO ₂ column and dissolved with 1 hexane/EtAcO (95:5) to obtain 4.00 g of a yellow solid product. The yield was 98%. LCMS (APCI+): calculated value of _{formula C 25} H ₂₀ O _2;

將化合物4-(4,12b-二氫二萘嵌苯-3-基)丁酸甲酯(1.00 g，4.36 mmol)及NBS (1.9 g，10.9 mmol)在無水DCM (45 mL)中之溶液混合物在室溫下攪拌並用氬氣淨化15分鐘，然後加入無水DMF (5 mL)。將所得混合物在室溫下攪拌3小時；TLC及LCMS顯示起始材料被消耗。加入20 mL水及50 mL DCM，將有機層用水沖洗數次，用MgSO₄ 乾燥，濃縮。將粗產物藉由SiO₂ 柱層析法純化，用1個己烷/EtAcO (95:5)溶離，得到1.25 g的二溴二萘嵌苯衍生物之兩種異構體之混合物，產率為56%。 Methyl 4-(4,9 -dibromo- 4,12b -dihydroperylene- 3 -yl ) butyrate /4-(4,10 -dibromo- 4,12b -dihydroperylene -3 -yl ) methyl butyrate

A solution of compound 4-(4,12b-dihydroperylene-3-yl)butyric acid methyl ester (1.00 g, 4.36 mmol) and NBS (1.9 g, 10.9 mmol) in anhydrous DCM (45 mL) The mixture was stirred at room temperature and purged with argon for 15 minutes, and then anhydrous DMF (5 mL) was added. The resulting mixture was stirred at room temperature for 3 hours; TLC and LCMS showed that the starting material was consumed. 20 mL of water and 50 mL of DCM were added, the organic layer was washed several times with water, dried with MgSO ₄ and concentrated. The crude product was purified by SiO ₂ column chromatography and eluted with 1 hexane/EtAcO (95:5) to obtain 1.25 g of a mixture of two isomers of dibromoperylene derivative, yield Is 56%.

LCMS (APCI+): _{Calculated value of formula C 25} H ₁₈ Br ₂ O ₂ ; actually measured value: 510.

將化合物4-(4,12b-二氫二萘嵌苯-3-基)丁酸甲酯(1.00 g，2.837 mmol，1當量)在無水DCM (20 mL)中之混合物置於兩頸燒瓶中，並保持在暗處。將混合物用氬氣淨化15分鐘，並分多個小部分加入NBS (1.767 g，9.929 mmol，3.5當量)，然後在室溫下攪拌15分鐘。加入無水DMF (10 mL)。將所得混合物在氬氣保護下在室溫下攪拌4小時。TLC及LCMS顯示起始材料已被消耗。加入25 mL水，分離有機層；將水層用乙酸乙酯再萃取，用水洗滌幾次，用MgSO₄ 乾燥，濃縮。將粗產物藉由SiO₂ 柱層析法純化，用己烷/DCM (9:1)至(1:4)溶離，得到0.655 g的三溴二萘嵌苯衍生物:二溴二萘嵌苯衍生物:四溴二萘嵌苯衍生物之三種異構體(7:1:0.5)之混合物。該產物不經進一步純化即用於下一步驟。產率為38%。LCMS (APCI+)：式C₂₅ H₁₇ Br₃ O₂ 之計算值；實測值：589。

Methyl 4-(4,9,10 -tribromoperylene- 3 -yl ) butyrate /4-(4,10 -dibromo- 4,12b -dihydroperylene- 3 -yl ) Methyl butyrate /4-(5,9,10 -tribromoperylene- 3 -yl ) methyl butyrate

A mixture of compound 4-(4,12b-dihydroperylene-3-yl)butyric acid methyl ester (1.00 g, 2.837 mmol, 1 equivalent) in anhydrous DCM (20 mL) was placed in a two-necked flask , And keep it in the dark. The mixture was purged with argon for 15 minutes, and NBS (1.767 g, 9.929 mmol, 3.5 equivalents) was added in small portions, and then stirred at room temperature for 15 minutes. Add dry DMF (10 mL). The resulting mixture was stirred at room temperature for 4 hours under the protection of argon. TLC and LCMS showed that the starting material has been consumed. 25 mL of water was added, and the organic layer was separated; the aqueous layer was re-extracted with ethyl acetate, washed with water several times, dried with MgSO ₄ and concentrated. The crude product was purified by SiO ₂ column chromatography and eluted with hexane/DCM (9:1) to (1:4) to obtain 0.655 g of tribromoperylene derivative: dibromoperylene Derivatives: A mixture of three isomers (7:1:0.5) of tetrabromoperylene derivatives. The product was used in the next step without further purification. The yield was 38%. LCMS (APCI+): calculated value of _{formula C 25} H ₁₇ Br ₃ O _2;

One isomer is shown for illustrative purposes. The actual reaction is a mixture of the brominated isomers of the starting material and the trifluoromethylated isomers of the product

Set up a 100 mL 2-neck round bottom flask. Add stirring rod, finned condenser and gas connection pipe. Flush the flask and condenser with argon. After stirring under argon protection, CuI (10.0 equivalents, 13.6 mmol, 2.586 g) was added to the flask. Under argon atmosphere, the perylene bromide isomer (1 equivalent, 1.36 mmol, 800 mg) was dissolved in 5 mL of anhydrous DMA, and transferred to the flask via a syringe. Rinse the vial with anhydrous DMA (2×5 mL) under argon atmosphere, and add these DMA aliquots to the reaction flask. Another 15 mL of anhydrous DMA was added to the reaction flask (total DMA=30 mL). Add methyl 2-(fluorosulfonyl)-2,2-difluoroacetate (10.0 equivalents, 13.6 mmol, 2.609 g, 1.509 g/mL, 1.73 mL) into the flask via a syringe, and seal the second neck with a glass stopper Department. The mixture was stirred and heated with a heating block set at 160°C. After 2 hours, LCMS indicated that the reaction was about 90% complete. CuI (5.0 equivalents, 6.80 mmol, 1295 mg) and methyl 2-(fluorosulfonyl)-2,2-difluoroacetate (5.0 equivalents, 6.80 mmol, 1306 mg, 1.509 g/mL, 0.866 mL) were added , And the reaction was stirred at 160°C for 2 hours, and then at room temperature overnight. The reaction mixture was processed as follows: the reaction mixture was poured into 700 mL of stirring water, and the reaction flask was washed with water and a small amount of methanol. The volume was adjusted to 900 mL with water, and the suspension was filtered through a thin layer of diatomaceous earth (slow filtration), and the filter cake was washed with water. After crushing the wet cake and filter paper, first stir in acetone (20 mL), and then add DCM (500 mL) with stirring. The organic layer was filtered through a second thin pad of diatomaceous earth, transferred to a separatory funnel and separated from water, dried over MgSO ₄ , filtered and concentrated to dryness. The mixture was purified by flash chromatography (first wavelength = 300 nm, second wavelength = 440 nm), 220 g column, equilibrated with 50% toluene/hexane, dissolved and loaded in 2:1 hexane:toluene , Use 50% (1 CV) à 100% toluene (10 CV) to dissolve. The desired fraction shows a strong UV peak at 440 nm.

The fractions are grouped into the early dissociated mixture, the middle peak and the late dissociated fractions. The early dissociation fraction was a trace amount of mixed Br/CF ₃ isomer, which was discarded. The middle peak is mainly tri-CF ₃ isomer, which is 204 mg (26.9% yield). The late dissociation fraction = di-CF ₃ , tri-CF ₃ and tetra-CF ₃ mixed isomers, 75 mg (10% yield).

¹ H NMR (400 MHz, 氯仿-d ) δ 8.35-8.28(m, 4H), 8.09 (d,J = 8.12 Hz, 2H), 8.08 (d,J = 8.08 Hz, 1H), 7.68 (d,J = 7.96 Hz, 1H)), 3.66 (s, 3H), 3.24 (t,J = 7.64 Hz, 2H), 2.36 (t,J = 7.44 Hz, 2H), 1.92 (q,J = 7.44 Hz, 2H)。

¹ H NMR (400 MHz, 氯仿-d ) δ 8.28 (d,J = 7.73 Hz, 1H), 8.23 (d,J = 7.4 Hz, 1H), 8.18 (d,J = 8.5 Hz, 1H)), 8.12-8.06 (m, 3H), 7.79 (t,J = 7.92 Hz, 1H), 7.73 (s,1H), 3.72 (s, 3H), 3.2 (t,J = 7.64 Hz, 2H), 2.5 (t,J = 7.44 Hz, 2H), 2.15 (q,J = 7.44 Hz, 2H)。The two isomers were separated into pure compounds; NMR and LCMS determined the two structures shown below:

¹ H NMR (400 MHz, chloroform- d ) δ 8.35-8.28(m, 4H), 8.09 (d, J = 8.12 Hz, 2H), 8.08 (d, J = 8.08 Hz, 1H), 7.68 (d, J = 7.96 Hz, 1H)), 3.66 (s, 3H), 3.24 (t, J = 7.64 Hz, 2H), 2.36 (t, J = 7.44 Hz, 2H), 1.92 (q, J = 7.44 Hz, 2H) .

¹ H NMR (400 MHz, chloroform- d ) δ 8.28 (d, J = 7.73 Hz, 1H), 8.23 (d, J = 7.4 Hz, 1H), 8.18 (d, J = 8.5 Hz, 1H)), 8.12 -8.06 (m, 3H), 7.79 (t, J = 7.92 Hz, 1H), 7.73 (s,1H), 3.72 (s, 3H), 3.2 (t, J = 7.64 Hz, 2H), 2.5 (t, J = 7.44 Hz, 2H), 2.15 (q, J = 7.44 Hz, 2H).

將4-(4,9,10-三(三氟甲基)二萘嵌苯-3-基)丁酸甲酯(40 mg，0.0718 mmol)、5M KOH水溶液(0.143 ml，0.718 mmol)、THF (2 ml)、MeOH (0.5 ml)之混合物在65℃下攪拌6小時。冷卻至0℃之後，將混合物用6N HCl水溶液酸化至pH=4-5，然後倒入水中，用DCM萃取，用MgSO₄ 乾燥，濃縮至乾燥，得到38 mg之紅色固體產物，產率為98%。產物不經進一步純化即用於下一步驟。 (4,9,10- Tris ( trifluoromethyl ) perylene- 3 -yl ) butyric acid

Mix 4-(4,9,10-tris(trifluoromethyl)perylene-3-yl) methyl butyrate (40 mg, 0.0718 mmol), 5M KOH aqueous solution (0.143 ml, 0.718 mmol), THF A mixture of (2 ml) and MeOH (0.5 ml) was stirred at 65°C for 6 hours. After cooling to 0°C, the mixture was acidified with 6N HCl aqueous solution to pH=4-5, then poured into water, extracted with DCM, dried with MgSO ₄ and concentrated to dryness to obtain 38 mg of red solid product with a yield of 98 %. The product was used in the next step without further purification.

LCMS (APCI+): _{Calculated value of formula C 27} H ₁₅ F ₉ O ₂ ; actually measured value: 542.40.

RLE-8 : ((T-4)-[2-[(4,5 -dihydro- 8- bromo -2H- benzo [g] indol- 2- ylidene- k N )-(3,5 - dimethyl-4 - (- ((4- (4,9, 10-tris (trifluoromethyl) perylene-3-yl) butoxy) oxy) phenyl) methyl] -4 ,5 -Dihydro- 1H- benzo [g] indolato- k N ] boron difluoride ) : derived from compound 6.2 (described above) [2-[(4,5-dihydro-8 -Bromo-2H-benzo[g]indol-2-ylidene-k N )-(3,5-dimethyl-4-hydroxyphenyl)methyl]-4,5-dihydro-1H- Benzo[g] indolato-k N ]boron difluoride (0.100 mmol, 52 mg) and ((4,9,10-trifluoromethyl)perylene-3-yl)butyric acid) (0.100 mmol, 55 mg) synthetic. The crude product was purified by flash chromatography on silica gel (80% toluene/hexane (1 CV)→100% toluene (5 CV)). The product-containing fractions were evaporated to dryness, yielding 77 mg (74% yield). MS (APCI): _{the calculated value of the chemical formula C 60} H ₄₀ BF ₁₁ N ₂ O ₂ (M-) = 1040; the measured value: 1040.

化合物 9.1 (3- 甲基 -4,5- 二氫 -1H- 苯并 [g] 吲哚 -2- 羧酸乙酯 ) ： 在250 mL之2頸圓底燒瓶中加入攪拌棒，並放至加熱塊中。向該燒瓶中加入1-四氫萘酮(100.0 mmol，14.620 g)及丙酸鈉(100.0 mmol，9.610 g)，之後加入乙酸(50 mL)。在敞開至空氣進行攪拌下將反應加熱至145℃。向40 mL螺旋蓋小瓶中加入2-(羥基亞胺基)-3-側氧基丁酸乙酯(2.50 mmol，398 mg)及Zn (粉，＜10 μm) (12.5 mmol，818 mg)。使此等物質在乙酸中成漿(12.5 mL)，並在約5分鐘之時段內分批加入含有酮之經攪拌反應中。對10.0 mmol之2-(羥基亞胺基)-3-側氧基丁酸酯及50.0 mmol之鋅粉的總體重複該過程三次。將反應在145℃下攪拌2.5小時，然後冷卻至室溫。將反應藉由在攪拌下倒入水(600 mL)中進行猝滅。用水使體積達至900 mL，然後用二氯甲烷(4×160 mL)萃取。將合併之有機層用水(100 mL)、鹽水(100 mL)洗滌，經MgSO₄ 乾燥，過濾，並蒸發至乾燥。在加熱下高真空移除大部分過量之1-四氫萘酮。將粗產物藉由在矽膠(5% EtOAc/己烷(1 CV)à20% EtOAc/己烷(10 CV))上進行快速層析法來純化。將含有產物之級分蒸發至乾，得到1.417 g (55%產率)。MS (APCI)：化學式C₁₆ H₁₇ NO₂ (M+H)之計算值=256，實測值：256。¹ H NMR (400 MHz) δ 8.98 (s, 1H), 7.35-7.31 (m, 1H), 7.27-7.21 (m, 2H), 7.20-7.15 (m, 1H), 4.34 (q,J = 7.1 Hz, 2H), 2.99-2.92 (m, 2H), 2.70-2.64 (m, 2H), 2.31 (s, 3H), 1.39 (t,J = 7.1 Hz, 3H)。 Example 2.9 RLE-9

Compound 9.1 (3- methyl -4,5 -dihydro- 1H- benzo [g] indole- 2- carboxylic acid ethyl ester ) : Add a stir bar to a 250 mL 2-neck round bottom flask and place it to In the heating block. To the flask were added 1-tetralone (100.0 mmol, 14.620 g) and sodium propionate (100.0 mmol, 9.610 g), followed by acetic acid (50 mL). The reaction was heated to 145°C while opening to air with stirring. Add ethyl 2-(hydroxyimino)-3-oxobutyrate (2.50 mmol, 398 mg) and Zn (powder, <10 μm) (12.5 mmol, 818 mg) to a 40 mL screw cap vial. These materials were slurried in acetic acid (12.5 mL) and added to the ketone-containing stirred reaction in portions over a period of about 5 minutes. Repeat this process three times for the total of 10.0 mmol of 2-(hydroxyimino)-3-oxobutyrate and 50.0 mmol of zinc powder. The reaction was stirred at 145°C for 2.5 hours and then cooled to room temperature. The reaction was quenched by pouring into water (600 mL) with stirring. Bring the volume to 900 mL with water, then extract with dichloromethane (4×160 mL). The combined organic layer was washed with water (100 mL), brine (100 mL), dried over MgSO ₄ , filtered, and evaporated to dryness. Under heating, high vacuum removes most of the excess 1-tetralone. The crude product was purified by flash chromatography on silica gel (5% EtOAc/hexane (1 CV)→20% EtOAc/hexane (10 CV)). The product-containing fractions were evaporated to dryness, yielding 1.417 g (55% yield). MS (APCI): _{The calculated value of the chemical formula C 16} H ₁₇ NO ₂ (M+H)=256, the measured value: 256. ¹ H NMR (400 MHz) δ 8.98 (s, 1H), 7.35-7.31 (m, 1H), 7.27-7.21 (m, 2H), 7.20-7.15 (m, 1H), 4.34 (q, J = 7.1 Hz , 2H), 2.99-2.92 (m, 2H), 2.70-2.64 (m, 2H), 2.31 (s, 3H), 1.39 (t, J = 7.1 Hz, 3H).

Compound 9.2 (3- methyl -4,5 -dihydro- 1H- benzo [g] indole ) : Add a stir bar to a 250 mL 2-neck round bottom flask, and install a finned condenser and gas Connecting pipe. The flask was flushed with argon, and compound 9.1 (5.01 mmol, 1.278 g) was added to the flask, followed by ethylene glycol (50 mL). To the reaction mixture was added KOH (in H ₂ O in 5.0 M, 25.03 mmol, 5.01 mL ). The reaction was stoppered and heated in a heating block at 100°C for 90 minutes under argon. Use heat to make the solution uniform. The temperature was increased to 160°C for 30 minutes and then cooled to 100°C. The reaction was quenched by pouring into stirred water (300 mL). The reaction was brought to a total volume of 500 mL with water, and then it was acidified with a 2.5 M acetic acid/2.5 M NaOAc (20 mL) solution. Use TFA to lower the pH to about 3.5. The resulting purple solid was filtered off, dried, and purified by flash chromatography on silica gel (5% EtOAc/hexane (1 CV)→20% EtOAc/hexane (10 CV)). The product-containing fractions were evaporated to dryness, yielding 767 mg (84% yield). MS (APCI): _{The calculated value of the chemical formula C 13} H ₁₃ N (M+H)=184, the measured value: 184. ¹ H NMR (400 MHz, acetonitrile- d ₃ ) δ 9.15 (s, 1H), 7.24 (d, J = 7.5 Hz, 1H), 7.20-7.13 (m, 2H), 7.00 (td, J = 7.4, 1.4 Hz, 1H), 6.52 (dd, J = 2.3, 0.9 Hz, 1H), 2.90-2.83 (m, 2H), 2.62-2.55 (m, 2H), 2.00 (s, 3H).

Compound 9.3 ((T-4)-[2-[(4,5 -Dihydro- 3 -methyl -2H- benzo [g] indol- 2- ylidene- κ N )(3,5- 二Methyl- 4 -hydroxyphenyl ) methyl ]-4,5 -dihydro- 3 -methyl -1H- benzo [g] indolato- κ N ] boron difluoride ) : with compound 3.2 In a similar manner, compound 9.3 was synthesized from compound 9.2 (3.97 mmol, 728 mg) and 4-hydroxy-2,6-dimethylbenzaldehyde (2.02 mmol, 304 mg). The crude product was purified by flash chromatography on silica gel (100% toluene (2 CV) à 10% EtOAc/toluene (10 CV)). The product-containing fractions were evaporated to give 563 mg (52% yield for 3 steps starting from pyrrole). MS (APCI): _{The calculated value of the chemical formula C 35} H ₃₁ BF ₂ N ₂ O (M+H)=544, the measured value: 544. ¹ H NMR (400 MHz, DMSO- d ₆ ) δ 9.61 (s, 1H), 8.62 (d, J = 7.9 Hz, 2H), 7.45-7.38 (m, 2H), 7.38-7.34 (m, 4H), 6.68 (s, 2H), 2.91-2.83 (m, 4H), 2.58-2.52 (m, 4H), 2.04 (s, 6H), 1.41 (s, 6H).

RLE-9 : ((T-4)-[2-[(4,5 -Dihydro- 3 -methyl -2H- benzo [g] indol- 2- ylidene- κ N )(3,5 - dimethyl-4 - ((4- (4,9, 10-tris (trifluoromethyl) perylene-3-yl) butoxy) oxy) phenyl) methyl] -4,5 - -1H- dihydro-3-methyl-benzo [g] indol-sulfato -κ N] boron difluoride): with the compound 2 (above) by the similar manner as the compound 9.3 (0.116 mmol, 63 mg) And (4,9,10-tris(trifluoromethyl)perylene-3-yl)butyric acid (0.116 mmol, 63 mg) to synthesize RLE-9. The crude product was purified by flash chromatography on silica gel (60% toluene/hexane (2 CV) à 100% toluene (isocratic)). The fraction containing the product (as a mixture of isomers) was evaporated to dryness, yielding 84 mg (68% yield). MS (APCI): _{the calculated value of the chemical formula C 62} H ₄₄ BF ₁₁ N ₂ O ₂ (M-) = 1068; the measured value: 1068.

化合物 10.1 ： 在室溫及氬氣氛圍下向3-甲基-4,5-二氫-1H-苯并[g]吲哚(3.55 mmol，652 mg)及4-羥基苯甲醛(1.77 mmol，216 mg)在無水1,2-二氯乙烷(35.0 mL)中之溶液中加入TFA (35.0 µL)。將反應混合物在室溫下攪拌70分鐘，冷卻至0℃，一次性加入對四氯苯醌(1.77 mmol，435 mg)，並繼續攪拌15分鐘。加入三乙胺(10.6 mmol，1.48 mL)，並在10分鐘內將該混合物加熱至室溫，然後加入BF₃ ·OEt₂ (15.9 mmol，1.96 mL)，並繼續攪拌75分鐘。加入更多的三乙胺(10.6 mmol，1.48 mL)及BF₃ ·OEt₂ (15.9 mmol，1.96 mL)，將混合物攪拌另外75分鐘，並減壓移除所有揮發物。將殘餘物用EtOAc (100 mL)稀釋，用1M HCl (2×100 mL)及6M HCl (100 mL)洗滌，乾燥(MgSO₄ )，並減壓濃縮。快速層析法(CH₂ Cl₂ )得到130 mg之10.1 (產率為17%)，為深藍色/綠色粉末。 Example 2.10 RLE-10

Compound 10.1 : Add 3-methyl-4,5-dihydro-1H-benzo[g]indole (3.55 mmol, 652 mg) and 4-hydroxybenzaldehyde (1.77 mmol, 216 mg) TFA (35.0 µL) was added to a solution in anhydrous 1,2-dichloroethane (35.0 mL). The reaction mixture was stirred at room temperature for 70 minutes, cooled to 0°C, p-tetrachlorobenzoquinone (1.77 mmol, 435 mg) was added in one portion, and stirring was continued for 15 minutes. Triethylamine (10.6 mmol, 1.48 mL) was added, and the mixture was heated to room temperature within 10 minutes, then BF ₃ ·OEt ₂ (15.9 mmol, 1.96 mL) was added, and stirring was continued for 75 minutes. More triethylamine (10.6 mmol, 1.48 mL) and BF ₃ ·OEt ₂ (15.9 mmol, 1.96 mL) were added, the mixture was stirred for another 75 minutes, and all volatiles were removed under reduced pressure. The residue was diluted with EtOAc (100 mL), washed with 1M HCl (2×100 mL) and 6M HCl (100 mL), dried (MgSO ₄ ), and concentrated under reduced pressure. Flash chromatography (CH ₂ Cl ₂ ) yielded 130 mg of 10.1 (17% yield) as a dark blue/green powder.

¹ H NMR (400 MHz, TCE-d ₂ ) δ 8.74 (d, J = 8.0 Hz, 2H), 7.43 (ddd, J = 8.5, 8.0, 1.7 Hz, 2H), 7.39-7.24 (m, 6H), 7.02 (d, J = 8.5 Hz, 2H), 5.05 (s, 1H), 2.89 (dd, J = 8.3, 5.9 Hz, 4H), 2.56 (dd, J = 8.3, 5.9 Hz, 4H), 1.44 (s , 6H).

RLE-10 : (T-4)-[2-[(4,5 -Dihydro- 8- bromo -2H- benzo [g] indol- 2- ylidene- κ N )-(4'-( 4-( Tris ( trifluoromethyl ) perylene- 3 -yl ) butoxy ) phenyl ) methyl ]-4,5 -dihydro- 1H- benzo [g] indolyl- κ N ] Boron difluoride: Add 10.1 (0.080 mmol, 41 mg), 4-(tris(trifluoromethyl)perylene-3-yl)butyric acid (0.084 mmol) at room temperature under argon atmosphere , 46 mg) and DMAP· p TsOH salt (0.160 mmol, 47 mg) in anhydrous 1,2-dichloroethane (10.0 mL) was added DIC (0.480 mmol, 75.0 µL), and the reaction mixture was Stir at room temperature for 2 hours and then at 50°C for 1 hour. The mixture was then cooled to room temperature, more 4-(tris(trifluoromethyl)perylene-3-yl)butyric acid (0.055 mmol, 30 mg) was added, and stirring was continued for 16 hours. The mixture was diluted with hexane (6.00 mL) and purified by flash chromatography (9:1 hexane/CH ₂ Cl ₂ → 3:7 hexane/CH ₂ Cl ₂ ) to obtain 73.7 mg of RLE- 10 (89% yield), dark purple powder.

¹ H NMR (400 MHz, TCE-d ₂ ) δ 8.76 (d, J = 8.1 Hz, 2H), 8.37-7.68 (m, 9H), 7.49-7.39 (m, 4H), 7.39-7.28 (m, 6H ), 3.49-3.30 (m, 2H), 2.99-2.77 (m, 5H), 2.77-2.67 (m, 1H), 2.61-2.49 (m, 4H), 2.40-2.26 (m, 1H), 2.20-2.08 (m, 1H), 1.42 (d, J = 7.6 Hz, 6H).

化合物 11.1 (4-( 二萘嵌苯 -3- 基 ) 丁酸 4- 甲醯基 -3,5- 二甲基苯基酯 ) ： 以與RLE-2 類似之方式，由4-羥基-2,6-二甲基苯甲醛(1.89 mmol，284 mg)及4-(二萘嵌苯-3-基)丁酸(0.946 mmol，320 mg)合成化合物11.1 。將粗產物藉由在矽膠(100%甲苯(5 CV)à10% EtOAc/甲苯(10 CV))上進行快速層析法純化。將含有產物之級分蒸發至乾。得到296 mg (66.5%產率)之橙色固體。MS (APCI)：化學式C₃₃ H₂₆ O₃ (M-)之計算值=470，實測值：470。¹ H NMR (400 MHz, TCE-d ₂ ) δ 10.52 (s, 1H), 8.25 (d,J = 7.5 Hz, 1H), 8.23-8.17 (m, 2H), 8.16 (d,J = 7.8 Hz, 1H), 7.94 (d,J = 8.4 Hz, 1H), 7.72 (d,J = 5.1 Hz, 1H), 7.70 (d,J = 5.1 Hz, 1H), 7.57 (t,J = 8.0 Hz, 1H), 7.51 (t,J = 7.8 Hz, 1H), 7.51 (t,J = 7.8 Hz, 1H), 7.40 (d,J = 7.7 Hz, 1H), 6.84 (s, 2H), 3.17 (t,J = 7.6 Hz, 2H), 2.72 (t,J = 7.2 Hz, 2H), 2.58 (s, 6H), 2.23 (p,J = 7.3 Hz, 2H)。 Example 2.11 Compound RLE-11

Compound 11.1 (4-( perylene- 3 -yl ) butyric acid 4 -methanyl- 3,5 -dimethylphenyl ester ) : In a similar manner to RLE-2 , it is composed of 4-hydroxy-2 Compound 11.1 was synthesized from ,6-dimethylbenzaldehyde (1.89 mmol, 284 mg) and 4-(perylene-3-yl)butyric acid (0.946 mmol, 320 mg). The crude product was purified by flash chromatography on silica gel (100% toluene (5 CV)→10% EtOAc/toluene (10 CV)). The product-containing fractions were evaporated to dryness. Obtained 296 mg (66.5% yield) of an orange solid. MS (APCI): _{The calculated value of the chemical formula C 33} H ₂₆ O ₃ (M-)=470, the measured value: 470. ¹ H NMR (400 MHz, TCE- d ₂ ) δ 10.52 (s, 1H), 8.25 (d, J = 7.5 Hz, 1H), 8.23-8.17 (m, 2H), 8.16 (d, J = 7.8 Hz, 1H), 7.94 (d, J = 8.4 Hz, 1H), 7.72 (d, J = 5.1 Hz, 1H), 7.70 (d, J = 5.1 Hz, 1H), 7.57 (t, J = 8.0 Hz, 1H) , 7.51 (t, J = 7.8 Hz, 1H), 7.51 (t, J = 7.8 Hz, 1H), 7.40 (d, J = 7.7 Hz, 1H), 6.84 (s, 2H), 3.17 (t, J = 7.6 Hz, 2H), 2.72 (t, J = 7.2 Hz, 2H), 2.58 (s, 6H), 2.23 (p, J = 7.3 Hz, 2H).

Compound RLE-11 (( T -4)-[2-[(4,5 -dihydro- 8- fluoro -2 H -benzo [ g ] indol- 2- ylidene- κ N )(3,5 - dimethyl-4- (4- (perylene 3-yl) butyrate) phenyl) methyl] -4,5-dihydro-8-fluoro -1 H - benzo [g] Indole- κ N ] boron difluoride ) : In a similar manner to compound 21, compound 21.2 (200 μmol), compound 11.1 (105 μmol, 49.4 mg), p-tetrachlorobenzoquinone (100 μmol, 24.5 mg) ), triethylamine (600 μmol, 84 μL) and BF ₃ .OEt _{2 to} synthesize compound RLE-11 . The crude product was purified by flash chromatography on silica gel (100% isocratic toluene). The product-containing fractions were evaporated to dryness. Obtained 74 mg (82% yield, based on compound 21.2). MS (APCI): _{The calculated value of the chemical formula C 58} H ₄₅ BF ₄ N ₂ O ₂ (M-)=888, the measured value: 888.

Example 2.12 RLE-12

3- Methyl -1,4- dihydroindeno [1,2- b ] pyrrole -2- carboxylic acid ethyl ester (12.1) was charged to 1-indanone (30.0 mmol, 3.96 g) at 180°C via a syringe pump ), Zn particles-20 mesh (50.0 mmol, 3.27 g) and sodium propionate (5.00 mmol, 480 mg) in the mixture of valeric acid (20.0 mL), add 2-(hydroxyimino)-3-oxo A solution of ethyl butyrate (10.0 mmol, 1.59 g) in valeric acid (10.0 mL) for 1 hour. After the addition was complete, the reaction mixture was stirred for another 15 minutes, then cooled to room temperature, and partitioned between 6 M hydrochloric acid (100 mL) and EtOAc (100 mL). The aqueous layer was extracted with EtOAc (3×100 mL), and the combined organics were washed with 1 M aqueous NaOH (3×200 mL), dried (MgSO ₄ ), and concentrated under reduced pressure. Reprecipitation from EtOH gave 505 mg of compound 12.1 (yield 21%) as a colorless solid.

¹ H NMR (400 MHz, chloroform- d ) δ 9.05 (br s, 1H), 7.48 (dt, J = 7.5, 1.1 Hz, 1H), 7.44 (dt, J = 7.5, 1.0 Hz, 1H), 7.30 ( td, J = 7.5, 1.0 Hz, 1H), 7.19 (td, J = 7.5, 1.1 Hz, 1H), 4.37 (q, J = 7.1 Hz, 2H), 3.49 (s, 2H), 2.42 (s, 3H ), 1.40 (t, J = 7.1 Hz, 3H).

3- methyl -1,4- dihydroindeno [1,2- b ] pyrrole ( compound 12.2) was added to compound 12.1 (0.1.61 mmol, 388 mg) and sodium hydroxide (4.82 mmol, 193 mg) in ethyl Water (500 µL) was added to the suspension in glycol (16 mL), and the reaction mixture was stirred at 150°C for 1 hour. Then it was cooled to room temperature, and 1.0 M _{aqueous NH 4} Cl solution (50.0 mL) was added. The precipitate was separated by vacuum filtration and air drying to obtain 264 mg of compound 12.2 (yield 97%) as a purple solid.

¹ H NMR (400 MHz, acetonitrile- d ₃ ) δ 9.17 (br s, 1H), 7.42 (d, J = 7.4 Hz, 1H), 7.35 (d, J = 7.5 Hz, 1H), 7.22 (dd, J = 7.4, 7.5 Hz, 1H), 7.03 (ddd, J = 7.5, 7.5, 1.2 Hz, 1H), 6.61 (dd, J = 2.3, 1.1 Hz, 1H), 3.38 (s, 2H), 2.11 (s, 3H).

4-( Perylene- 3 -yl ) butyric acid 4-(6,6 -difluoro- 13,15 -dimethyl- 12,16 -dihydro- 6H-5l4,6l4- indeno [2',1':4,5] pyrrolo [1,2-c] indeno [2',1':4,5] pyrrolo [2,1-f][1,3,2] boron Alkyl- 14 -yl )-3,5- dimethylphenyl ester (RLE-12) under argon atmosphere to compound 12.2 (0.467 mmol, 79.0 mg) and p TsOH·H ₂ O (0.005 mmol) at room temperature under argon atmosphere , 1.00 mg) Compound 12.3 (0.212 mmol, 100 mg) was added to a solution in anhydrous 1,2-dichloroethane (5.00 mL). The reaction mixture was stirred at room temperature for 3 hours, and then cooled to 0°C, p-tetrachlorobenzoquinone (0.212 mmol, 52.0 mg) was added in one portion, and stirring was continued for 15 minutes. Triethylamine (1.27 mmol, 177 µL) was added, and the mixture was heated to room temperature within 10 minutes, then BF ₃ ·OEt ₂ (1.91 mmol, 235 µL) was added, and stirring was continued for another 30 minutes. The reaction mixture was diluted with EtOAc (30.0 mL), washed with 1M HCl (3×30.0 mL) and saturated aqueous NaCl (30.0 mL), dried (MgSO ₄ ) and concentrated under reduced pressure. Flash chromatography (toluene) yielded 96.0 mg of RLE-12 (54% yield) as a dark purple powder.

¹ H NMR (400 MHz, chloroform- d ) δ 8.39 (d, J = 7.8 Hz, 2H), 8.27-8.13 (m, 4H), 7.96 (d, J = 8.4 Hz, 1H), 7.68 (dd, J = 8.1, 4.3 Hz, 2H), 7.56 (t, J = 7.9 Hz, 1H), 7.51-7.44 (m, 6H), 7.41 (d, J = 7.7 Hz, 1H), 7.38-7.33 (m, 2H) , 6.92 (s, 2H), 3.51 (s, 4H), 3.21 (t, J = 7.5 Hz, 2H), 2.73 (t, J = 7.1 Hz, 2H), 2.22 (s, 8H), 1.47 (s, 6H).

在氬氣氛圍下在室溫下向12.2 (0.086 mmol，15.0 mg)及p TsOH·H₂ O (1個晶體)在無水CH₂ Cl₂ (0.90 mL)中之溶液中加入13.1 (0.039 mmol，26.0 mg)。將反應混合物在室溫下攪拌1小時，然後將其冷卻至0℃，一次性加入對四氯苯醌(0.039 mmol，10.0 mg)，並繼續攪拌15分鐘。加入三乙胺(0.234 mmol，33.0 µL)，並在10分鐘內將該混合物加熱至室溫，然後加入BF₃ ·OEt₂ (0.351 mmol，43.0 µL)，並繼續攪拌另外30分鐘。將反應混合物用EtOAc (5.00 mL)稀釋，用1M HCl (3×5.00 mL)及飽和NaCl水溶液(5.00 mL)洗滌，乾燥(MgSO₄ )並減壓濃縮。快速層析法(甲苯)得到16.0 mg之RLE-13 (產率為38%)，為暗紫色/綠色粉末。 Example 2.13 RLE-13

To a solution of 12.2 (0.086 mmol, 15.0 mg) and p TsOH·H ₂ O (1 crystal) in anhydrous CH ₂ Cl ₂ (0.90 mL) was added 13.1 (0.039 mmol, 26.0 mg). The reaction mixture was stirred at room temperature for 1 hour, then cooled to 0°C, p-tetrachlorobenzoquinone (0.039 mmol, 10.0 mg) was added in one portion, and stirring was continued for 15 minutes. Triethylamine (0.234 mmol, 33.0 µL) was added, and the mixture was heated to room temperature within 10 minutes, then BF ₃ ·OEt ₂ (0.351 mmol, 43.0 µL) was added, and stirring was continued for another 30 minutes. The reaction mixture was diluted with EtOAc (5.00 mL), washed with 1M HCl (3×5.00 mL) and saturated aqueous NaCl (5.00 mL), dried (MgSO ₄ ) and concentrated under reduced pressure. Flash chromatography (toluene) gave 16.0 mg of RLE-13 (38% yield) as a dark purple/green powder.

¹ H NMR (400 MHz, chloroform- d ) δ 8.40 (d, J = 7.9 Hz, 2H), 8.34-7.62 (m, 8H), 7.53-7.42 (m, 4H), 7.36 (apparent t, J = 7.5 Hz, 2H), 7.02-6.93 (m, 2H), 3.52 (s, 4H), 3.41-3.31 (m, 2H), 2.85-2.74 (m, 2H), 2.37-2.22 (m, 8H), 1.52 (s, 6H).

Example 2.14 RLE-14

3,3 -Dimethyl -2,3 -dihydro- 1H- inden- 1 -one (RLE-14.1) A solution of 3-methyl crotonic acid (19.0 mmol, 1.90 g) in benzene (10.0 mL) _{Slowly add to AlCl 3} (57.0 mmol, 7.60 g) in a 100 mL round bottom flask. The resulting mixture was heated to reflux for 5 hours, cooled to 0°C, quenched with 1M HCl (50.0 mL) and extracted with EtOAc (3×50.0 mL). The combined organics were washed with saturated aqueous NaHCO ₃ (3×100 mL) and saturated aqueous NaCl (100 mL), dried (MgSO ₄ ) and concentrated under reduced pressure. Flash chromatography (9:1, hexane/EtOAc) yielded 2.62 g of 14.1 (86% yield) as an orange oil.

¹ H NMR (400 MHz, chloroform- d ) δ 7.72-7.67 (m, 1H), 7.65-7.57 (m, 1H), 7.53-7.47 (m, 1H), 7.39-7.32 (m, 1H), 2.60- 2.58 (m, 2H), 1.47-1.36 (m, 6H); ¹³ C NMR (101 MHz, Chloroform- d ) δ 205.7, 163.7, 135.1, 134.8, 127.2, 123.4, 123.2, 52.8, 38.4, 29.8.

3,4,4 -trimethyl -1,4- dihydroindeno [1,2- b ] pyrrole -2- carboxylic acid ethyl ester (14.2) was adjusted to 14.1 (3.12 mmol, 500 mg), Zn particles-20 mesh (15.6 mmol, 1.02 g) and sodium propionate (1.56 mmol, 150 mg) are added to the mixture of valeric acid (12.5 mL) with 2-(hydroxyimino)-3- A solution of ethyl pendant oxybutyrate (4.68 mmol, 750 mg) in valeric acid (2.50 mL) lasts for 1 hour. After the addition was complete, the reaction mixture was stirred for another 15 minutes, then cooled to room temperature, and partitioned between 6 M hydrochloric acid (25.0 mL) and EtOAc (25.0 mL). The aqueous layer was extracted with EtOAc (3×25.0 mL), the combined organics were dried (MgSO ₄ ) and concentrated under reduced pressure. Flash chromatography (9:1, hexane/EtOAc) yielded 42 mg of 14.2 (5% yield) as a colorless solid.

¹ H NMR (400 MHz, chloroform- d ) δ 9.19 (s, 1H), 7.40-7.34 (m, 2H), 7.27-7.18 (m, 2H), 4.38 (q, J = 7.1 Hz, 2H), 2.47 (s, 3H), 1.51 (s, 6H), 1.40 (t, J = 7.1 Hz, 3H).

3,4,4 -trimethyl -1,4- dihydroindeno [1,2- b ] pyrrole (14.3) to 14.2 (0.149 mmol, 42 mg) and sodium hydroxide (0.446 mmol, 18.0 mg) in Water (50.0 µL) was added to the suspension in ethylene glycol (1.50 mL), and the reaction mixture was stirred at 150°C for 1 hour. Then it was cooled to room temperature, and 1.0 M _{aqueous NH 4} Cl solution (5.00 mL) was added. The mixture was extracted with CH ₂ Cl ₂ (3×10.0 mL) to obtain 29 mg of 12.2 (99% yield) as a purple solid.

¹ H NMR (400 MHz, chloroform- d ) δ 7.97 (br s, 1H), 7.30 (dt, J = 7.3, 0.9 Hz, 1H), 7.21-7.14 (m, 2H), 7.07 (ddd, J = 7.4 , 5.4, 3.3 Hz, 1H), 6.57 (dd, J = 2.2, 1.1 Hz, 1H), 2.20 (d, J = 1.0 Hz, 3H), 1.50 (s, 6H).

4-( Tris ( trifluoromethyl ) perylene- 3 -yl ) butyric acid 4-(6,6 -difluoro- 12,12,13,15,16,16- hexamethyl- 12,16 - dihydro ^{-6 H -5 λ 4, 6 λ} 4 - indeno [2 ', 1': 4,5] pyrrolo [1,2- c] indeno [2 ', 1': 4,5] Pyrrolo [2,1- f ][1,3,2] diazepine- 14 -yl )-3,5- dimethylphenyl ester (RLE-14) 14.3 (0.071 mmol, 14.0 mg) and p TsOH·H ₂ O (1 crystal) were added to a solution of 13.1 (0.039 mmol, 26.0 mg) _{in anhydrous CH 2} Cl _{2 (0.70 mL).} The reaction mixture was stirred at room temperature for 1 hour, then cooled to 0°C, p-tetrachlorobenzoquinone (0.036 mmol, 9.00 mg) was added in one portion, and stirring was continued for 15 minutes. Triethylamine (0.216 mmol, 30.0 µL) was added, and the mixture was heated to room temperature within 10 minutes, then BF ₃ ·OEt ₂ (0.324 mmol, 40.0 µL) was added, and stirring was continued for another 30 minutes. The reaction mixture was diluted with EtOAc (5.00 mL), washed with 1M HCl (3×5.00 mL) and saturated aqueous NaCl (5.00 mL), dried (MgSO ₄ ) and concentrated under reduced pressure. Flash chromatography (1:1 hexane/toluene→toluene) yielded 8.00 mg of RLE-14 (21% yield), which was a dark purple/green powder.

¹ H NMR (400 MHz, chloroform- d ) δ 8.34-7.62 (m, 10H), 7.46-7.33 (m, 6H), 7.01-6.92 (m, 2H), 3.42-3.31 (m, 2H), 2.79 ( dt, J = 13.9, 7.0 Hz, 2H), 2.36-2.23 (m, 8H), 1.53 (s, 6H), 1.50 (s, 12H).

化合物 15.1 (7- 溴 -3- 甲基 -4,5- 二氫 -1H- 苯并 [g] 吲哚 -2- 羧酸乙酯 ) ： 向250 mL之2頸圓底燒瓶中加入攪拌棒、6-溴-3,4-二氫萘-1(2H)-酮(20.0 mmol，4.502 g)、丙酸鈉(5.00 mmol，480 mg)及鋅(顆粒，10-20目，50.0 mmol，3.270 g)。該燒瓶上裝有帶翅片之冷凝器及氣體連接管。用氬氣沖洗燒瓶，並加入丙酸(20 mL)。在丙酸(10 mL)中製備乙醯乙酸乙酯-2-肟(10.0 mmol，1.591 g)溶液。將反應燒瓶置於鋁加熱塊中，並預熱至160℃。在60分鐘之時段內經由注射器泵加入乙醯乙酸乙酯-2-肟溶液。粗製品LCMS表明產物及脫氫鹵化之產物以及未反應之起始材料及脫氫鹵化之起始材料。將粗製反應混合物冷卻至室溫，然後用EtOAc (200 mL)稀釋。將反應混合物轉移至分液漏斗並用水(1×200 mL、1×100 mL)、1N NaOH水溶液(2×50 mL)及鹽水(50 mL)洗滌。將有機層經MgSO₄ 乾燥，過濾，並濃縮成油狀物。將該油狀物用己烷(50 mL)稀釋，並使其在室溫下靜置隔夜。將所得晶體濾出，用己烷洗滌。將母液蒸發至乾燥，並藉由在矽膠(100%己烷(2 CV)à10% EtOAc/己烷(20 CV))上進行快速層析法來純化。將含有產物之級分蒸發至乾。將自矽膠中純化之產物與上述晶體合併，以得到純的產物。¹ H NMR表明兩個吡咯-Me基團以約1:2之比率存在。LCMS表明主產物為脫氫鹵化之產物。得到1.077 g (產率為約38.2%，基於具有來自¹ H NMR之比率的共混MW)。兩者在矽膠上為密不可分開的。不經進一步純化即用於下一步驟。MS (APCI)：化學式C₁₆ H₁₆ BrNO₂ (M+H)之計算值=334，實測值：334。MS (APCI)：化學式C₁₆ H₁₇ NO₂ (M+H)之計算值=256，實測值：256。¹ H NMR (400 MHz, TCE-d ₂ ) δ 9.00 (s, 1H), 7.41-7.12 (m, 3.7H), 4.34 (q,J = 7.1 Hz, 2H), 3.00-2.88 (m, 2H), 2.72-2.59 (m, 2H), 2.31 (s, 2H, H-異構體), 2.30 (s, 1H, Br-異構體), 1.39 (td,J = 7.1, 1.2 Hz, 3H)。

Example 2.15 Compound 15.1 :

Compound 15.1 (7- Bromo- 3 -methyl -4,5 -dihydro- 1H- benzo [g] indole- 2- carboxylic acid ethyl ester ) : Add a stir bar to a 250 mL 2-neck round bottom flask , 6-bromo-3,4-dihydronaphthalene-1(2H)-one (20.0 mmol, 4.502 g), sodium propionate (5.00 mmol, 480 mg) and zinc (granules, 10-20 mesh, 50.0 mmol, 3.270 g). The flask is equipped with a finned condenser and a gas connection pipe. Flush the flask with argon and add propionic acid (20 mL). Prepare a solution of ethyl acetate-2-oxime (10.0 mmol, 1.591 g) in propionic acid (10 mL). The reaction flask was placed in an aluminum heating block and preheated to 160°C. The ethyl acetate-2-oxime solution was added via a syringe pump over a period of 60 minutes. The crude product LCMS indicates the product and the dehydrohalogenated product as well as the unreacted starting material and the dehydrohalogenated starting material. The crude reaction mixture was cooled to room temperature and then diluted with EtOAc (200 mL). The reaction mixture was transferred to a separatory funnel and washed with water (1×200 mL, 1×100 mL), 1N NaOH aqueous solution (2×50 mL) and brine (50 mL). The organic layer was dried over MgSO ₄ , filtered, and concentrated to an oil. The oil was diluted with hexane (50 mL) and allowed to stand overnight at room temperature. The obtained crystals were filtered off and washed with hexane. The mother liquor was evaporated to dryness and purified by flash chromatography on silica gel (100% hexane (2 CV) à 10% EtOAc/hexane (20 CV)). The product-containing fractions were evaporated to dryness. The product purified from the silica gel is combined with the above crystals to obtain a pure product. ¹ H NMR indicated the presence of two pyrrole-Me groups in a ratio of approximately 1:2. LCMS indicated that the main product was the product of dehydrohalogenation. Obtained 1.077 g (yield of about 38.2%, based on blended MW with a ratio ^{from 1 H NMR).} The two are inseparable on the silicone. It was used in the next step without further purification. MS (APCI): _{The calculated value of the chemical formula C 16} H ₁₆ BrNO ₂ (M+H)=334, the measured value: 334. MS (APCI): _{The calculated value of the chemical formula C 16} H ₁₇ NO ₂ (M+H)=256, the measured value: 256. ¹ H NMR (400 MHz, TCE- d ₂ ) δ 9.00 (s, 1H), 7.41-7.12 (m, 3.7H), 4.34 (q, J = 7.1 Hz, 2H), 3.00-2.88 (m, 2H) , 2.72-2.59 (m, 2H), 2.31 (s, 2H, H-isomer), 2.30 (s, 1H, Br-isomer), 1.39 (td, J = 7.1, 1.2 Hz, 3H).

3- methyl -4,5 -dihydro- 1 H -benzo [ g ] indole and 7- bromo- 3 -methyl -4,5 -dihydro- 1 H -benzo [ g ] indole ( 15.2) To 3-methyl-4,5-dihydro- 1H -benzo[ g ]indole-2-carboxylic acid ethyl ester and 7-bromo-3-methyl-4,5-dihydro-1 H -benzo[ g ]indole-2-carboxylic acid ethyl ester (approximately 2:1 ratio, 2.87 mmol, 812 mg) in a _{mixture of 30:1 ethylene glycol/H 2} O (25.0 mL) Sodium hydroxide (7.29 mmol, 120 mg) was added, and the mixture was stirred at 150°C for 4 hours. It was then cooled to room temperature and quenched with 1M NH ₄ Cl solution (150 mL), and the pH was adjusted with 6M HCl to pH = 3. The precipitate was collected by vacuum filtration and lyophilized for 16 hours to obtain 639 mg of 3-methyl-4,5-dihydro-1 H -benzo[ g ]indole and 7-bromo-3-methyl- An inseparable mixture of 4,5-dihydro- 1H -benzo[ g ]indole (approximately 2:1 ratio, quantitative yield), and the inseparable mixture was used in subsequent synthesis steps without further purification.

( T -4)-[2-[(4,5 -Dihydro- 3 -methyl -7- bromo -2 H -benzo [ g ] indol- 2- ylidene- κ N )-(2',6' -Dimethyl- 4'-(4-( perylene ) butoxy ) phenyl ) methyl )-4,5 -dihydro- 3 -methyl -7- bromo -1 H- Benzo [ g ] indolato- κ N ] boron difluoride (RLE-15) to 3-methyl-4,5-dihydro as described above in CH ₂ Cl _{2 (14.0 mL)} -1 H -benzo[ g ]indole and 7-bromo-3-methyl-4,5-dihydro-1 H -benzo[ g ]indole (300 mg, about 1.42 mmol) 15.3 (0.568 mmol, 267 mg) and p TsOH·H ₂ O (0.057 mmol, 7.00 mg), and the reaction mixture was stirred at room temperature for 2 hours. Then tetrachloro-p-benzoquinone (0.568 mmol, 140 mg) was added, and the mixture was stirred at room temperature for 15 minutes. Triethylamine (3.41 mmol, 474 µL) was added, the mixture was stirred at room temperature for 30 minutes, then BF ₃ ·OEt ₂ (5.11 mmol, 631 µL) was added, and the mixture was stirred at room temperature for 1 hour. The mixture was then diluted with EtOAc (50.0 mL), washed with 3M HCl (3×50.0 mL), dried (MgSO ₄ ) and concentrated under reduced pressure. Flash chromatography (4:1 toluene/hexane→9:1 toluene/hexane) yielded 105 mg of RLE-15 (18% yield) as a dark blue/purple solid.

¹ H NMR (400 MHz, chloroform- d ) δ 8.78 (d, J = 8.1 Hz, 1H), 8.66 (d, J = 8.8 Hz, 1H), 8.27-8.13 (m, 4H), 7.96 (d, J = 8.4 Hz, 1H), 7.68 (dd, J = 8.1, 4.4 Hz, 2H), 7.59-7.37 (m, 7H), 7.31 (apparent t, J = 7.4 Hz, 1H), 6.90 (s, 2H) , 3.21 (t, J = 7.5 Hz, 2H), 2.94-2.81 (m, 4H), 2.72 (t, J = 7.2 Hz, 2H), 2.57-2.48 (m, 4H), 2.33-2.22 (m, 2H) ), 2.18 (s, 6H), 1.35 (d, J = 3.1 Hz, 6H).

化合物 15.4A (3- 側氧基 -3-( 二萘嵌苯 -3- 基 ) 丙酸甲酯 ) ： 在500 mL之3頸圓底燒瓶中加入攪拌棒，並用氬氣沖洗。向該燒瓶中加入AlCl₃ (9.52 mmol，1.27 g)，之後加入無水二氯甲烷(160 mL)。將溶液在室溫下攪拌，並加入3-氯-3-側氧基丙酸甲酯(8.30 mmol，0.890 mL)，之後加入二萘嵌苯(7.92 mmol，1.99 g)。將反應在氬氣下在室溫下攪拌隔夜。第二天早晨，使燒瓶安裝有翅片式空氣冷凝器，並用加熱塊加熱至45℃，並在氬氣下於該溫度下攪拌整個週末。加入另一部分3-氯-3-側氧基丙酸甲酯(8.30 mmol，0.890 mL)，並在氬氣下在45℃下繼續攪拌隔夜。藉由加入水(100 mL)及6N HCl水溶液(100 mL)猝滅反應，並用二氯甲烷(100 mL)稀釋。將各層分離(乳液)，並將水層用DCM (2×200 mL，乳液)，然後用DCM (4×100 mL)萃取。將有機層用MgSO₄ 乾燥，過濾並真空濃縮。將產物藉由在矽膠上(100% DCM (3 CV)à1% EtOAc/DCM (0 CV)à1% EtOAc/DCM (3 CV)à10% EtOAc/DCM (8 CV))進行的快速層析法而純化，得到1.905 g之產物(68%產率)。MS (APCI)：C₂₄ H₁₆ O₃ (M+H)之計算值=353；實測值：353。 Example RLE-16 Regarding the Synthesis of 16.1:

Compound 15.4A (3 -oxo- 3-( perylene- 3 -yl ) methyl propionate ) : Add a stir bar to a 500 mL 3-neck round bottom flask and flush with argon. _{AlCl 3} (9.52 mmol, 1.27 g) was added to the flask, followed by dry dichloromethane (160 mL). The solution was stirred at room temperature, and methyl 3-chloro-3-oxopropionate (8.30 mmol, 0.890 mL) was added, followed by perylene (7.92 mmol, 1.99 g). The reaction was stirred overnight at room temperature under argon. The next morning, the flask was fitted with a finned air condenser and heated to 45°C with a heating block, and stirred at this temperature under argon for the whole weekend. Another portion of methyl 3-chloro-3-oxopropionate (8.30 mmol, 0.890 mL) was added, and stirring was continued overnight at 45°C under argon. The reaction was quenched by adding water (100 mL) and 6N aqueous HCl (100 mL) and diluted with dichloromethane (100 mL). The layers were separated (emulsion), and the aqueous layer was extracted with DCM (2×200 mL, emulsion), then DCM (4×100 mL). The organic layer was dried over MgSO _4, filtered and concentrated in vacuo. The product was subjected to flash chromatography on silica gel (100% DCM (3 CV)→1% EtOAc/DCM (0 CV)→1% EtOAc/DCM (3 CV)→10% EtOAc/DCM (8 CV)). Purification yielded 1.905 g of product (68% yield). MS (APCI): _{calculated value of C 24} H ₁₆ O ₃ (M+H)=353; measured value: 353.

Compound 15.4B (3-( perylene- 3 -yl ) propionic acid ) : Compound 42.1 (3.10 mmol, 1.091 g) was reduced with triethylsilane and saponified in a similar manner to compound 41.1. The resulting acid has very poor solubility and requires hot THF to dissolve in a reasonable volume. 682 mg was obtained (68% yield in 2 steps). MS (APCI): _{calculated value of C 23} H ₁₆ O ₂ (MH)=323; measured value: 323.

Compound 15.4C (3-( Perylene- 3 -yl ) propionic acid 4-(4,4,5,5 -tetramethyl -1,3,2- dioxaborolan- 2- yl ) benzene Base ester ) : from compound 42.2 (1.67 mmol, 543 mg) and 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol (2.51 mmol , 553 mg) Compound 42.3 was synthesized. The 40 mL screw cap vial was flushed with argon and filled with compound 42.2 (1.67 mmol, 543 mg), 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborane -2-yl)phenol (2.51 mmol, 553 mg), DMAP (0.214 mmol, 26 mg), pTsOH.H ₂ O (0.193 mmol, 36 mg) and a stir bar. The vial was sealed with a screw cap septum, anhydrous DCM (4 mL) was added, and the mixture was stirred to form a solution. To the stirred reaction was added DIC (0.642 mmol, 0.100 mL), and the mixture was stirred under argon overnight. The reaction mixture was diluted with ethyl acetate (150 mL) and extracted with 3N aqueous HCl (25 mL). The organic layer was washed with saturated aqueous sodium bicarbonate (25 mL), brine (15 mL), dried over MgSO ₄ , filtered and concentrated in vacuo. This material is purified by flash chromatography on silica gel (100% DCM (3 CV)→1% EtOAc/DCM (0 CV)→10% EtOAc/DCM (10 CV)) so that it can be After purification by flash chromatography, the product was obtained, which was 434 mg (49% yield). MS (APCI): _{Calculated value of C 35} H ₃₁ BO ₄ (MH)=525; measured value: 525.

( T -4)-[2-[(4,5 -Dihydro- 3 -methyl- 7-((4-( perylene ) butoxy ) phenyl ) methyl- 2 H -benzene and [g] indol-2-ylidene - κ N) - (2 ' , 6'- dimethyl-4' - (4- (perylene-based) butoxy) phenyl) methyl - ] -4,5-dihydro-3-methyl-7 - ((4- (perylene-based) butoxy) phenyl) methyl -1 H - benzo [g] indol-sulfato - κ N ] Boron difluoride (RLE-16) to RLE-15 (0.049 mmol, 50.0 mg) and 15.4 (0.107 mmol, 58.0 mg) in 6:3:1 THF/toluene/water (1.00 mL) PdCl ₂ (dppf) (0.002 mmol, 1.80 mg) and K ₂ CO ₃ (0.147 mmol, 20.0 mg) were added to the solution, and the reaction mixture was heated to reflux for 16 hours, then cooled to room temperature and used Quench with 1 M HCl (6.00 mL). The mixture was extracted with CH ₂ Cl ₂ (3×5.00 mL), the combined organics were dried (MgSO ₄ ) and concentrated under reduced pressure. Flash chromatography (toluene→49:1 toluene/EtOAc)) gave 26.0 mg of RLE-16 (31% yield) as a blue solid.

¹ H NMR (400 MHz, methylene chloride- d ₂ ) δ 8.79 (dd, J = 18.7, 8.3 Hz, 2H), 8.30-8.13 (m, 8H), 8.00 (d, J = 8.4 Hz, 2H) , 7.83-7.38 (m, 18H), 7.37-7.05 (m, 6H), 6.92 (s, 2H), 3.21 (td, J = 7.8, 4.6 Hz, 4H), 2.98 (t, J = 7.0 Hz, 2H ), 2.91 (t, J = 7.1 Hz, 2H), 2.78-2.70 (m, 4H), 2.58 (dt, J = 15.1, 7.0 Hz, 4H), 2.35-2.11 (m, 10H), 1.38 (d, J = 2.7 Hz, 6H).

Example 2.17 RLE-17

( T -4)-[2-[(4,5 -Dihydro- 3 -methyl- 2 H -benzo [ g ] indol- 2- ylidene- κ N )-(2',6'- Dimethylphenyl ) methyl ]-4,5 -dihydro- 3 -methyl- 1 H -benzo [ g ] indolato- κ N ] boron difluoride and ( T -4)-[ 2-[(4,5 -Dihydro- 3 -methyl -7- bromo -2 H -benzo [ g ] indol- 2- ylidene- κ N )-(2',6' -dimethyl Phenyl ) methyl ]-4,5 -dihydro- 3 -methyl -7- bromo -1 H -benzo [ g ] indolato- κ N ] boron difluoride (17.2) in CH ₂ 3-methyl-4,5-dihydro- 1H -benzo[ g ]indole prepared as described above in Cl ₂ (10.0 mL) and 7-bromo-3-methyl-4,5-di Hydrogen-1 H -benzo[ g ]indole (248 mg, about 1.17 mmol) and p TsOH·H ₂ O (0.039 mmol, 5.00 mg) were added to the mixture of ₂ in CH 2 Cl ₂ (2.00 mL) ,6-dimethylbenzaldehyde (0.391 mmol, 52 mg), and the reaction mixture was stirred at room temperature for 1 hour. Then tetrachloro-p-benzoquinone (0.391 mmol, 96.0 mg) was added, and the mixture was stirred at room temperature for 20 minutes. Triethylamine (2.34 mmol, 326 µL) was added, the mixture was stirred at room temperature for 30 minutes, then BF ₃ ·OEt ₂ (3.52 mmol, 434 µL) was added, and the mixture was stirred at room temperature for 1 hour. More triethylamine (1.17 mmol, 163 µL) was added, and after stirring at room temperature for 10 minutes, BF ₃ ·OEt ₂ (1.76 mmol, 217 µL) was added, and the mixture was stirred at room temperature for another 30 minutes . The mixture was then diluted with EtOAc (50.0 mL), washed with 3M HCl (3×50.0 mL), dried (MgSO ₄ ) and concentrated under reduced pressure. Flash chromatography (1:1, toluene/hexane) yielded 133 mg of ( T -4)-[2-[(4,5-dihydro-3-methyl-2 H -benzo[ g ]indole Dole-2-ylidene-κ N )-(2',6'-dimethylphenyl)methyl]-4,5-dihydro-3-methyl-1 H -benzo[ g ]indole Root-κ N ]boron difluoride and ( T -4)-[2-[(4,5-dihydro-3-methyl-7-bromo-2 H -benzo[ g ]indole-2 -Subunit-κ N )-(2',6'-Dimethylphenyl)methyl]-4,5-dihydro-3-methyl-7-bromo-1 H -benzo[ g ]in Dologen-κ N ] boron difluoride (ratio of about 2:1) is a dark blue/purple solid, which is used in subsequent synthesis steps without further purification.

( T -4)-[2-[(4,5 -Dihydro- 3 -methyl- 7-((4-( perylene ) butoxy ) phenyl ) methyl- 2 H -benzene And [ g ] indol- 2- ylidene - κ N )-(2',6' -dimethylphenyl ) methyl ]-4,5 -dihydro- 3 -methyl- 7-((4 - (perylene phenyl) butoxy) phenyl) methyl -1 H - benzo [g] indol-sulfato - κ N] boron difluoride (RLE-17) to a solution of 6: 3: 1 ( T -4)-[2-[(4,5-Dihydro-3-methyl-7-bromo-2 H -benzo[ g ]Indol-2-ylidene-κ N )-(2',6'-dimethylphenyl)methyl]-4,5-dihydro-3-methyl-7-bromo-1 H- _{Add PdCl 2} (dppf) (0.010 mmol, 7.00 mg) to a mixture of benzo[ g ]indolato-κ N ]boron difluoride (133 mg, about 0.194 mmol) and 17.3 (0.426 mmol, 230 mg) And K ₂ CO ₃ (0.582 mmol, 80.0 mg), and the reaction mixture was heated to reflux for 16 hours, then it was cooled to room temperature and quenched with 1 M HCl (10.0 mL). The mixture was extracted with CH ₂ Cl ₂ (3×10.0 mL), and the combined organics were dried (MgSO ₄ ) and concentrated under reduced pressure. Flash chromatography (4:1 toluene/hexane→toluene) gave 51.0 mg of RLE-17 (10% total yield) as a dark blue/purple solid.

¹ H NMR (400 MHz, dichloromethane- d ₂ ) δ 8.90-8.71 (m, 2H), 8.30-8.16 (m, 3H), 8.04-7.97 (m, 1H), 7.80-7.63 (m, 4H) , 7.60-7.40 (m, 5H), 7.36-7.26 (m, 2H), 7.25-7.15 (m, 3H), 3.20 (t, J = 7.7 Hz, 2H), 3.09-2.84 (m, 4H), 2.75 (t, J = 7.2 Hz, 2H), 2.70-2.45 (m, 4H), 2.33-2.11 (m, 8H), 1.36 (s, 6H).

Example 2.18 RLE-18

1,4,5,6 -Tetrahydrobenzo [6,7] cycloheptano [1,2-b] pyrrole (18.1) to 1-benzocycloheptanone (10.0 mmol, 1.46 mL) at room temperature _{) Add NH 2} OH·HCl (15.0 mmol, 1.04 g) and sodium acetate (25.0 mmol, 2.05 g) to a 3:1 H ₂ O/EtOH (32.5 mL) solution, and add the reaction mixture to 95 Stir at °C for 1 hour. Then it was cooled to room temperature, filtered, washed with water (150 mL) and freeze-dried for 16 hours to obtain 1.64 g of 6,7,8,9-tetrahydro-5H-benzo[7]cycloheptene-5- Ketone oxime (94% yield) is a colorless solid, and the solid is used in subsequent synthesis steps without further purification.

Add KOH to a solution of 6,7,8,9-tetrahydro-5H-benzo[7]cyclohepten-5-one oxime (5.71 mmol, 1.00 g) in DMSO (9.00 mL) at room temperature (17.1 mmol, 959 mg), and heat the reaction mixture to 140°C, and then add 1,2-dichloroethane (11.4 mmol, 897 µL) in DMSO (2.00 mL) via a syringe pump within 3 hours . The mixture was then cooled to room temperature, quenched with 1M _{aqueous NH 4} Cl (30.0 mL) and extracted with CH ₂ Cl ₂ (3×30.0 mL). The combined organics were dried (MgSO ₄ ) and concentrated under reduced pressure. Flash chromatography (hexane→9:1 hexane/EtOAc) gave 262 mg of compound 18.1 (yield 25%) as a yellow solid.

¹ H NMR (400 MHz, chloroform-d) δ 8.18 (br s, 1H), 7.34 (dd, J = 7.8, 1.3 Hz, 1H), 7.25-7.19 (m, 1H), 7.16 (dd, J = 7.6 , 1.6 Hz, 1H), 7.13-7.07 (m, 1H), 6.84 (t, J = 2.8 Hz, 1H), 6.17 (t, J = 2.8 Hz, 1H), 2.91 (t, J = 6.8 Hz, 2H ), 2.86-2.80 (m, 2H), 2.07-1.98 (m, 2H); ¹³ C NMR (101 MHz, chloroform-d) δ 140.4, 131.8, 129.3, 126.8, 125.9, 125.2, 123.2, 121.8, 118.3, 111.1, 34.9, 27.8, 26.7.

4-(19,19 -Difluoro- 6,7,11,12,13,19 -hexahydro- 5H-18λ4,19λ4 -benzo [3',4'] cycloheptano [1',2' :4,5] pyrrolo [1,2-c] benzo [3',4'] cycloheptano [1',2':4,5] pyrrolo [2,1-f][1, 3,2] Diazaborane- 9- yl )-3,5 -difluorophenol (18.2) to compound 18.1 (1.36 mmol, 250 mg) and 2,6-difluoro-4-hydroxybenzaldehyde (0.650 mmol, 103 mg) _{pTsOH·H 2} O (0.065 mmol, 8 mg) was added to a solution _{in CH 2} Cl ₂ (13.5 mL), and the reaction mixture was stirred at room temperature for 1 hour. Then DDQ (0.780 mmol, 177 mg) was added, and the mixture was stirred at room temperature for 1 hour. Triethylamine (3.90 mmol, 542 µL) was added, the mixture was stirred at room temperature for 1 hour, then BF ₃ ·OEt ₂ (5.85 mmol, 722 µL) was added, and the mixture was stirred at room temperature for 1 hour. More triethylamine (3.90 mmol, 542 µL) was added, and after stirring at room temperature for 30 minutes, BF ₃ ·OEt ₂ (5.85 mmol, 722 µL) was added, and the mixture was stirred at room temperature for another 1 hour . The mixture was then diluted with EtOAc (30.0 mL), washed with 3M HCl (3×30.0 mL), dried (MgSO ₄ ) and concentrated under reduced pressure. Flash chromatography (toluene→19:1 toluene/EtOAc) gave 149 mg of compound 18.2 (42% yield) as a blue solid.

¹ H NMR (400 MHz, DMSO-d6) δ 7.73 (d, J = 7.4 Hz, 1H), 7.31-7.14 (m, 4H), 6.71 (s, 1H), 6.62 (d, J = 10.0 Hz, 1H ), 2.47-2.40 (m, 2H), 2.28-2.04 (m, 2H), 1.90-1.83 (m, 3H).

4-( Tris ( trifluoromethyl ) perylene- 3 -yl ) butyric acid 4-(19,19 -difluoro- 6,7,11,12,13,19 -hexahydro- 5H-18λ4, 19λ4 -Benzo [3',4'] cycloheptano [1',2':4,5] pyrrolo [1,2-c] benzo [3',4'] cycloheptano [1 ',2': 4,5] pyrrolo [2,1-f][1,3,2] diazepine- 9- yl )-3,5 -difluorophenyl ester (RLE-18) To compound 18.2 (0.091 mmol, 50 mg), 4-(4,9,10-tris(trifluoromethyl)perylene-3-yl)butyric acid (0.099 mmol, 54 mg) and DMAP·pTsOH salt DIC (0.364 mmol, 57 µL) was added to a solution of (0.091 mmol, 27 mg) in CH ₂ Cl ₂ (0.50 mL), and the reaction mixture was stirred at room temperature for 1 hour. The reaction mixture was then filtered through Celite and concentrated under reduced pressure. Flash chromatography (4:1 toluene/hexane→toluene) gave 77 mg of RLE-18 (78% yield) as a dark purple solid.

¹ H NMR (400 MHz, chloroform-d) δ 8.28-8.01 (m, 7H), 7.85-7.77 (m, 1H), 7.37-7.28 (m, 4H), 7.25-7.12 (m, 4H), 7.01- 6.89 (m, 2H), 6.59-6.51 (m, 2H), 3.44-3.31 (m, 2H), 2.92-2.78 (m, 2H), 2.67-2.56 (m, 4H), 2.41-2.21 (m, 6H) ), 2.08-1.99 (m, 4H).

Example 2.19 RLE-19

4-( Tris ( trifluoromethyl ) perylene- 3 -yl ) butyric acid 3,5- dichloro- 4 -methanylphenyl ester (19.1) to 2,6-dichloro-4-hydroxy Benzaldehyde (0.335 mmol, 64 mg), 4-(tris(trifluoromethyl)perylene-3-yl)butyric acid (0.369 mmol, 200 mg) and DMAP·pTsOH salt (0.034 mmol, 10 mg) DIC (1.34 mmol, 210 µL) was added to CH ₂ Cl ₂ (1.68 mL), and the reaction mixture was stirred at room temperature for 2 hours. The reaction mixture was then filtered through Celite and concentrated under reduced pressure. Flash chromatography (toluene) gave 187 mg of compound 19.1 (78% yield) as a yellow solid.

¹ H NMR (400 MHz, chloroform-d) δ 10.50-10.33 (m, 1H), 8.48-7.50 (m, 8H), 7.19-7.14 (m, 2H), 3.45-3.25 (m, 2H), 2.83- 2.59 (m, 2H), 2.33-2.03 (m, 2H).

4-( Tris ( trifluoromethyl ) perylene- 3 -yl ) butyric acid 3,5- dichloro- 4-(19,19 -difluoro- 6,7,11,12,13,19- Hexahydro- 5H-18λ4,19λ4 -benzo [3',4'] cycloheptano [1',2':4,5] pyrrolo [1,2-c] benzo [3',4' ] Cycloheptano [1',2':4,5] pyrrolo [2,1-f][1,3,2] diazepine- 9- yl ) phenyl ester (RLE-19) To a solution of compound 19.1 (0.461 mmol, 84 mg) and compound 18.1 (0.210 mmol, 150 mg) in CH ₂ Cl ₂ (4.50 mL) was added pTsOH·H ₂ O (0.021 mmol, 3 mg), and reacted The mixture was stirred at room temperature for 1 hour. Then DDQ (0.252 mmol, 57 mg) was added, and the mixture was stirred at room temperature for 1 hour. Triethylamine (1.26 mmol, 175 µL) was added, the mixture was stirred at room temperature for 1 hour, then BF ₃ ·OEt ₂ (1.89 mmol, 233 µL) was added, and the mixture was stirred at room temperature for 2 hours. The mixture was then diluted with EtOAc (30.0 mL), washed with 3M HCl (3×30.0 mL), dried (MgSO ₄ ) and concentrated under reduced pressure. Flash chromatography (4:1 toluene/hexane→toluene) gave 106 mg of RLE-19 (yield 45%) as a purple solid.

¹ H NMR (400 MHz, dichloromethane-d ² ) δ 8.61-7.60 (m, 10H), 7.39-7.11 (m, 8H), 6.54-6.40 (m, 2H), 3.46-3.30 (m, 2H) , 2.90-2.55 (m, 6H), 2.39-2.09 (m, 6H), 2.08-1.94 (m, 4H).

Example 2.20 RLE-20

4-( Tris ( trifluoromethyl ) perylene- 3 -yl ) butyryl chloride (20.1) to 4-(tris(trifluoromethyl)perylene-3-yl)butyric acid (0.500 mmol , 271 mg) were added DMF (1 drop) and oxalic chloride (1.00 mmol, 86 µL) to a solution of CH2Cl2 (2.50 mL), and the reaction mixture was stirred at room temperature for 1.5 hours. All volatiles were removed under reduced pressure to obtain 252 mg of compound 20.1 (90% yield) as a yellow/brown solid. This material has sufficient purity to be directly used in subsequent synthesis steps.

6,6 -Difluoro- 13,15 -dimethyl- 14-(3-(4,9,10- tris ( trifluoromethyl ) perylene- 3 -yl ) propyl )-12,16 - dihydro -6H-5 λ 4,6 λ 4- indeno [2 ', 1': 4,5] pyrrolo [1,2-c] indeno [2 ', 1': 4,5] pyrrolo and [2,1-f] [1,3,2] ] diazepin-borane (RLE-20) to the compound 20.1 (0.250 mmol, 140 mg) in CH ₂ Cl ₂ (0.50 mL) at room temperature Add a solution of 3-methyl-1,4-dihydroindeno[1,2-b]pyrrole (0.550 mmol, 93 mg) in CH ₂ Cl ₂ (0.75 mL) to the solution, and add the reaction mixture to Stir at room temperature for 2 hours, after which a second portion of 3-methyl-1,4-dihydroindeno[1,2-b]pyrrole (0.270 mmol, 45 mg) is added and the mixture is stirred for another 1 hour . Triethylamine (1.50 mmol, 208 µL) was added, the mixture was stirred at room temperature for 30 min, then BF ₃ ·OEt ₂ (2.25 mmol, 278 µL) was added, and the mixture was stirred at room temperature for 16 hours. The mixture was then diluted with EtOAc (10.0 mL), washed with 3M HCl (3×10.0 mL), dried (MgSO ₄ ) and concentrated under reduced pressure. Flash chromatography (7:3 hexane/toluene→toluene) yielded 29 mg of RLE-20 (13% yield) as a purple solid.

2-(4-(3-(6,6 -Difluoro- 13,15 -dimethyl- 12,16 -dihydro- 6H-5λ4,6λ4- indeno [2',1':4,5] Pyrrolo [1,2-c] indeno [2',1':4,5] pyrrolo [2,1-f][1,3,2] diazepine- 14 -yl ) propyl ) Phenyl )-6-(4-( diphenylamino ) phenyl )-1H- benzo [de] isoquinoline- 1,3(2H) -dione (RLE-21) at room temperature to 21.1 (0.200 mmol, 124 mg) in DCE (2.20 mL) was added 3-methyl-1,4-dihydroindeno[1,2-b]pyrrole (0.440 mmol, 74 mg) in DCE (2.20 mL) mL), and the reaction mixture was heated to reflux for 16 hours, after which it was cooled to room temperature. Triethylamine (1.20 mmol, 166 µL) was added, the mixture was stirred at room temperature for 1 hour, then BF ₃ ·OEt ₂ (1.80 mmol, 222 µL) was added, and the mixture was stirred at room temperature for 3.5 hours. The mixture was then diluted with EtOAc (30.0 mL), washed with 3M HCl (3×30.0 mL), dried (MgSO ₄ ) and concentrated under reduced pressure. Flash chromatography (3:2 hexane/EtOAc, then 1:1 toluene/CH ₂ Cl ₂ ) gave 13 mg of RLE-21 (7% yield) as a purple solid.

¹ H NMR (400 MHz, dichloromethane-d ² ) δ 8.6 (d, J = 7.5 Hz, 2H), 8.5 (d, J = 8.5 Hz, 1H), 8.3 (d, J = 7.7 Hz, 2H) , 7.8-7.7 (m, 2H), 7.5 (d, J = 7.6 Hz, 2H), 7.5-7.4 (m, 6H), 7.4-7.3 (m, 10H), 7.2-7.2 (m, 6H), 7.1 -7.1 (m, 2H), 3.6 (s, 2H), 3.2-3.1 (m, 2H), 3.0 (t, J = 7.2 Hz, 2H), 2.4 (s, 6H), 2.2-2.1 (m, 2H ).

Example 3 Preparation of filter layer A glass substrate was basically prepared in the following manner. Cut a 1.1 mm thick glass substrate measuring 1 inch x 1 inch into a certain size. Then the glass substrate was washed with detergent and deionized (DI) water, rinsed with fresh deionized water, and ultrasonically treated for about 1 hour. The glass was then immersed in isopropyl alcohol (IPA) and ultrasonicated for about 1 hour. Then the glass substrate was immersed in acetone and ultrasonically processed for about 1 hour. The glass was then removed from the acetone bath and dried with nitrogen at room temperature.

Preparation of poly(methyl methacrylate) (PMMA) (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

Add the 20% PMMA solution (4 g) prepared above to 3 mg of the photoluminescent composite prepared as described above in a sealed container, 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, the sample was covered with aluminum foil to prevent the sample from being exposed to light. In this way, three samples were prepared separately for each of emission/FWHM and quantum yield. The spin-coated sample was baked in a vacuum oven at 80°C for 3 hours to evaporate the remaining solvent.

Insert a 1 inch x 1 inch sample into a Shimadzu UV-3600 UV-VIS-NIR spectrophotometer (Shimadzu Instruments, Inc., Columbia, MD, USA). All equipment operations are performed in a nitrogen-filled glove box. The obtained absorption/emission spectrum of PC-8 is shown in Figure 1, and the obtained absorption/emission spectrum of PC-33 is shown in Figure 2.

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

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

512 24 ＜1% 對比例2

592 37 ＜1% RLE-1

640 27 -- RLE-2

643 28 77% RLE-3

649 27 89% RLE-4

626 26 87% RLE-5

643 23 87% RLE-6

601 32 86% RLE-7

578 31 92% RLE-8

643 28 79% RLE-9

627 26 85% RLE-10   

628 27 81% RLE-11

630 26 83.3% RLE-12

619 21 94.6% RLE-13

620 22 89.2% RLE-14

624 21 87.9% RLE-15

632 25 78.3% RLE-16

646 31 82.8% RLE-17

643 29 82.4% RLE-18

615 34 79% RLE-19

612 35 83.5% RLE-20

622 25 65.4% The results of film characterization (absorption peak wavelength, FWHM and quantum yield) are shown in Table 1 below. Table 1. Cpd number structure Emission in PMMA (nm) FWHM (nm) Φ at 450 nm (PMMA) Comparative example 1

512 twenty four ＜1% Comparative example 2

592 37 ＜1% RLE-1

640 27 - RLE-2

643 28 77% RLE-3

649 27 89% RLE-4

626 26 87% RLE-5

643 twenty three 87% RLE-6

601 32 86% RLE-7

578 31 92% RLE-8

643 28 79% RLE-9

627 26 85% RLE-10

628 27 81% RLE-11

630 26 83.3% RLE-12

619 twenty one 94.6% RLE-13

620 twenty two 89.2% RLE-14

624 twenty one 87.9% RLE-15

632 25 78.3% RLE-16

646 31 82.8% RLE-17

643 29 82.4% RLE-18

615 34 79% RLE-19

612 35 83.5% RLE-20

622 25 65.4%

Light stability test procedure: A PMMA film with a dye concentration of 2×10 ^-3 M is used to evaluate the light stability of the film. The PMMA film used for stability is the same film used for the measurement of all optical properties previously provided. 90.0 ml of cyclopentanone was added to 30.0 g of polymethylmethacrylate (PMMA) polymer (Milipore-Sigma, St. Louis, MO, USA) and stirred at 50°C for several days. The obtained substrate solution was cast on a pre-cleaned (washed with soap and water) glass substrate (1 inch by 1 inch by 1 inch) by a casting machine set at the gap of the casting blade of 200 microns. During casting, the cast film was kept under the cover for 30 minutes, and thereafter for another 30 minutes. Then put the cast glass surface on the hot plate and bake it at 120°C for about 20 minutes.

Use blue LED light (supplier: inspired LED) with emission peak at 465 nm as the light source. Place the blue LED strip on a U-shaped channel with a size of 1"×12", and place a commercially available diffuser (unknown by the supplier) on the top of the U-shaped channel to obtain a uniform light distribution. Place a membrane with a size of 1"×x1" on top of the diffuser. The average irradiance at the film is about 1.5 mW/cm ² . The device is in the surrounding environment.

Before and after exposing the film to LED light for 165 hours, 330 hours, and 500 hours, respectively, the absorption at the peak absorption wavelength was measured. Measure film absorption by UV-vis 3600 (Shimadzu)

The remaining absorption measured after each exposure period is divided by the light stability of the absorption indicator film before exposure.

The amount of additive (LA-57) is 0.2% by weight.

LA-57Depends on the amount of 20% PMMA solution. If you use X ml PMMA solution to make the dye solution. Weigh 0.4X mg of additive and add it to a 10 ml vial. Add 100 microliters of toluene to dissolve the additives, and then add the solution containing the additives to the PMMA dye solution. Ultrasonic treatment for 10 minutes. (LA-57, purchased from the supplier: Adeka, Ni(AcAc)2, DABCO are all purchased from sigma Aldrich)

LA-57

絕對% (λ最大) 100% 86% 84% -16% QY(λ最大) 0.769 0.493 0.466    RLE-6

絕對% (λ最大) 100% 92% 89% -11% QY(λ最大) 0.861 0.666 0.589    RLE-8   

絕對% (λ最大) 100% 82% 79% -21% QY(λ最大) 0.787 0.667 0.554    RLE-9   

絕對% (λ最大) 100% 87% 80% -20% QY(λ最大) 0.854 0.67 0.631    RLE-9+0.2% LA-57    絕對% (λ最大) 100% -- 86% -14% QY(λ最大) 0.866 -- 0.783    RLE-10   

絕對% (λ最大) 100% -- 77% -23% QY(λ最大) 0.808 -- 0.778    RLE-11

絕對% (λ最大) 100% 89% 83% -17% QY(λ最大) 0.833 0.604 0.483    RLE-13

異構體之混合物 絕對% (λ最大) 100% 88% 83% -17% QY(λ最大) 0.892 0.844 0.79    RLE-14

絕對% (λ最大) 100% 93% 91% -9% QY(λ最大) 0.879 0.875 0.895    The results are depicted in the table below: Composition (0.2% in PMMA) 0 hours 165 hours 330 hours Decrease% (330 hours) RLE-2

Absolute% (λmax) 100% 86% 84% -16% QY (λmax) 0.769 0.493 0.466 RLE-6

Absolute% (λmax) 100% 92% 89% -11% QY (λmax) 0.861 0.666 0.589 RLE-8

Absolute% (λmax) 100% 82% 79% -twenty one% QY (λmax) 0.787 0.667 0.554 RLE-9

Absolute% (λmax) 100% 87% 80% -20% QY (λmax) 0.854 0.67 0.631 RLE-9+0.2% LA-57 Absolute% (λmax) 100% - 86% -14% QY (λmax) 0.866 - 0.783 RLE-10

Absolute% (λmax) 100% - 77% -twenty three% QY (λmax) 0.808 - 0.778 RLE-11

Absolute% (λmax) 100% 89% 83% -17% QY (λmax) 0.833 0.604 0.483 RLE-13

Mixture of isomers Absolute% (λmax) 100% 88% 83% -17% QY (λmax) 0.892 0.844 0.79 RLE-14

Absolute% (λmax) 100% 93% 91% -9% QY (λmax) 0.879 0.875 0.895

The terms used in the present invention and the appended embodiments (for example, the subject 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 Is interpreted as "at least", the term "includes" shall be interpreted as "including but not limited to" etc.). In addition, if a specific number of elements is introduced, this can be interpreted as including at least the number described, as can be dictated by the context (for example, the expression "two narrative 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 such items. For example, the phrase "A or B": should be understood to include the possibility of "A" or "B" or "A and B".

Unless otherwise specified herein or clearly contradictory to the context, the terms "a", "an", "the" and similar indicators used in the context of describing the present invention (especially in the context of the following embodiments) Should be interpreted as covering both the singular and the plural. The use of any and all examples or exemplary language (such as "for example") provided herein is only intended to better illustrate the present invention, and is not intended to limit the scope of any implementation. Any language in the specification should not be construed as indicating that any unrepresented element is indispensable for the practice of the present invention.

The grouping of alternative elements or embodiments disclosed herein should not be construed as a limitation. 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 attached 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 implementation manners described in these descriptions 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 implementation includes all modifications and equivalents of the subject described in the implementation that are permitted by applicable laws. In addition, unless otherwise stated herein or clearly contradictory to 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 in accordance with the teachings herein. Therefore, the embodiments are not limited to exactly as shown and described.

FIG. 1 is a graph depicting the absorption spectrum and emission spectrum of an embodiment of the photoluminescent composite. FIG. 2 is a graph depicting the absorption spectrum and emission spectrum of an embodiment of the photoluminescent composite.

Claims (20)

A photoluminescent composite, the photoluminescent composite is represented by the following formula: A—(L—D) _1-3 , where each D is a donor chromophore, wherein the donor chromophore absorbs blue light The light with the first wavelength in the range releases excitation energy in response thereto, wherein the above-mentioned donor chromophore is:

; Wherein R ⁸ , R ¹⁰ and R ^{11 are} independently H or CF ₃ ; wherein A is an acceptor chromophore, and the acceptor chromophore includes a boron dipyrromethene (BODIPY) derivative, wherein the acceptor The chromophore absorbs the excitation energy released by the donor chromophore, wherein the acceptor chromophore subsequently emits light having a second wavelength longer than the first wavelength; and each L is a linking group; And the emission quantum yield of the photoluminescence composite is greater than 80%. Such as the photoluminescent composite of claim 1, where: A is:

[Formula III], wherein each R'is independently H, -CH ₃ , F or CF ₃ ; R" is -H, or a bond connected to L-D; R ¹ and R ^{2 are} independently H or -CH ₃ ; R ³ and R ^{4 are} independently H, F, Br, -CF ₃ , phenyl substituted by 1 or 2 -CH ₃ , -F, -CF ₃ , or connected to L— The bond of D; X is -CH ₂ -, -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -C(R ^a ) ₂ -, -CHC(R ^a )-, -C(=O) -, -O-, -S-, -C(Ar) ₂ -, -C(CH ₂ Ar) ₂ -, spiro-cycloalkyl group or aromatic spiro-polycyclic group, wherein R ^a Is a C ₁ -C ₄ alkyl group and wherein Ar is an aryl group or a heteroaryl group; wherein at least one of R″ ^{, R 3 or R 4} is a bond to LD; and L is Optionally substituted C ₄ -C ₇ ester or C ₃ -C ₅ keto ester. The photoluminescent composite of claim 1 or 2, wherein when X is spiro-cyclopentane. Such as the photoluminescent composite of claim 1 or 2, where L is:

. Such as the photoluminescent composite of claim 1 or 2, where L is:

. The photoluminescent composite of claim 1 or 2, wherein the photoluminescent composite is:

. A color conversion film, the color conversion film includes: Transparent substrate layer; and A color conversion layer, wherein the color conversion layer includes a resin matrix, and Such as the photoluminescent composite of claim 1, 2, 3, 4, 5 or 6, wherein the photoluminescent composite is dispersed in the resin matrix. Such as the color conversion film of claim 7, the color conversion film also contains a singlet oxygen quencher. Like the color conversion film of claim 7, the color conversion film also contains a radical scavenger. The color conversion film of claim 7, wherein the thickness of the color conversion film is between about 1 µm and about 200 µm. The color conversion film of claim 7, wherein the color conversion film absorbs blue light with a wavelength of 400 nm to 480 nm and emits red light with a wavelength of 575 nm to 650 nm. The color conversion film of claim 11, wherein the color conversion film emits red light with a wavelength of 600 nm to 650 nm. The color conversion film of 8, 9, 10, 11, or 12, wherein the color conversion film has a light stability of at least 80% after being exposed to blue light with a peak wavelength of 465 nm for 165 hours. The color conversion film of 8, 9, 10, 11, or 12, wherein the color conversion film has a light stability of at least 75% after being exposed to blue light with a peak wavelength of 465 nm for 330 hours. A method for preparing a color conversion film as claimed in claim 7, 8, 9, 10, 11, 12, 13 or 14, the above method comprising: Apply the mixture to the surface of the transparent substrate; Wherein the above mixture comprises the photoluminescent composite of claim 1, 2, 3, 4, 5 or 6 and a resin matrix dissolved in a solvent. The method of claim 15, wherein the photoluminescence composite has an absorbance with a wavelength in the range of 400 nm to 480 nm and an emission with a wavelength in the range of 575 nm to 650 nm. The method of claim 15, wherein the mixture also contains a free radical scavenger, and the free radical scavenger is dissolved in the solvent. The method of claim 15, wherein the mixture also contains a singlet oxygen quencher, and the singlet oxygen quencher is dissolved in the solvent. A backlight unit comprising the color conversion film of claim 7, 8, 9, 10, 11, 12, 13, or 14. A display device including the backlight unit as claimed in claim 19.

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