CN115003778A

CN115003778A - Boron-containing cyclic light-emitting compound and color conversion film comprising same

Info

Publication number: CN115003778A
Application number: CN202180009558.4A
Authority: CN
Inventors: 郑世俊; 杰弗瑞·R·汉默克; 刘协; 史丹尼斯劳·端瓦尔; 伊安·萨斯卡; 蔡洁; 王鹏
Original assignee: Nitto Denko Corp
Current assignee: Nitto Denko Corp
Priority date: 2020-01-17
Filing date: 2021-01-14
Publication date: 2022-09-02
Also published as: TW202132539A; JP7415016B2; JP2023510880A; WO2021146380A1; KR20220116256A; TWI764521B

Abstract

The present invention relates to a novel photoluminescent complex comprising a BODIPY moiety covalently bonded to a blue light absorbing moiety, as well as a color conversion film, a backlight unit using the color conversion film.

Description

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

Cross Reference to Related Applications

The present application claims benefit of U.S. provisional application No.62/962,626 filed on day 17, 2020 and U.S. provisional application No.63/008,284 filed on day 10, 4, 2020, which are incorporated herein by reference in their entirety.

Technical Field

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

Background

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

As high definition large screen displays become more and more popular, the demand for higher performance, thinner and powerful displays is also increasing. Current Light Emitting Diodes (LEDs) are obtained by exciting a green phosphor, a red phosphor or a yellow phosphor by a blue light source to obtain a white light source. However, the full width at half maximum (FWHM) of the emission peaks of current green and red phosphors is quite large, typically greater than 40nm, resulting in green and red spectra overlapping and appearing in colors that are not completely distinguishable from each other. This overlap results in poor color reproduction and degradation of the color gamut.

In order to correct for the deterioration of the color gamut, a method of using a film containing quantum dots in combination with an LED has been developed. However, the use of quantum dots is problematic. First, cadmium-based quantum dots are extremely toxic and are banned from use in many countries due to health safety issues. Second, the efficiency of non-cadmium quantum dots to convert blue LED light to green and red light is very low. Third, quantum dots require expensive encapsulation processes to protect against moisture and oxygen. Finally, the cost of using quantum dots is high due to the difficulty in controlling the dimensional uniformity during the production process.

One new approach to solving the problems that arise when using quantum dots involves the use of dipyrromethene Boron (BODIPY) compounds as luminescent materials in place of quantum dots.

Disclosure of Invention

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

Means for solving the problems

Some embodiments include a photoluminescent composition comprising: a donor chromophore; an acceptor chromophore; and a linker complex. Some photoluminescent complexes are represented by formula I:

A—(L—D) _1-3 [ formula I ]]。

In some embodiments, the donor chromophore or D absorbs light within the blue wavelength and emits excitation energy. The donor chromophore may include a perylene derivative of the following formula:

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.

In some embodiments, the acceptor chromophore or a emits light within the red wavelengths. The acceptor chromophore may include a BODIPY derivative of the formula:

in some embodiments, R' is independently H, -CH ₃ F, or CF ₃ (ii) a R' is-H, or a bond to L-D; r ¹ And R ² Independently is H or-CH ₃ ；R ³ And R ⁴ Independently H, F, Br, -CF ₃ Optionally with 1 or 2-CH ₃ 、-F、-CF ₃ Substituted phenyl, or an 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 or aromatic spiro-polycyclic radical, in which R is ^a Is C ₁ -C ₄ Alkyl, and wherein Ar is aryl or heteroaryl; and L is optionally substituted C ₄ -C ₇ Esters or C ₃ -C ₅ A ketoester.

In some embodiments, the acceptor chromophore absorbs the excitation energy emitted by the donor chromophore, wherein the acceptor chromophore subsequently emits light at a second wavelength, which is a higher wavelength of light than blue light. In some embodiments, the acceptor chromophore emits light within the red wavelengths. The linker complex connects the donor chromophore and the acceptor chromophore.

In some embodiments, the photoluminescent complex has an emission quantum yield greater than 80%.

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

In some embodiments, the photoluminescent composite can have a Stokes shift (Stokes shift), i.e., the difference between the excitation peak of the blue light absorbing moiety and the excitation of the BODIPY moiety is equal to or greater than 45 nm.

Some embodiments include a color conversion film that 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 color conversion film may comprise a thickness 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 400nm to about 480nm and emit red light in the wavelength range of 575nm to about 650 nm. In some embodiments, the color conversion film may further comprise a transparent substrate layer. Some embodiments include a color conversion film having a photostability of at least 80% after 165 hours of exposure to blue light having a peak wavelength of 465 nm. Other embodiments include a color conversion film having a photostability of at least 75% after 330 hours exposure to blue light having a peak wavelength of 465 nm. In some embodiments, the transparent substrate layer of the color conversion film comprises two opposing surfaces, wherein the color conversion layer is disposed on one of the opposing surfaces.

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

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

Some embodiments describe a display device comprising a backlight unit as described herein.

These and other embodiments are described in more detail below.

Drawings

Fig. 1 is a graph depicting the absorption and emission spectra of one embodiment of a photoluminescent composite.

Fig. 2 is a graph depicting the absorption and emission spectra of one embodiment of a photoluminescent composite.

Detailed Description

The present invention describes a photoluminescent complex and its use in color conversion films. The photoluminescent composition can be used to improve and enhance the transmission of more than one desired emission bandwidth within a color conversion film. In one embodiment, the photoluminescent composition can simultaneously increase the transmission of the desired first emission bandwidth and decrease the transmission of the second emission bandwidth. In some embodiments, the photoluminescent composition can simultaneously increase the transmission of the desired first emission bandwidth and decrease the transmission of the second emission bandwidth. For example, the color conversion film may increase the contrast or intensity between two or more colors, thereby increasing the distinction between each other. Some embodiments include a photoluminescent composition that can increase the contrast or intensity between two colors, thereby increasing their discrimination from one another.

The use of the term "may" should be understood as "being" or "not being", or alternatively "doing" or "not doing" or "would not". For example, the expression "alkyl may be substituted" should be interpreted as, for example, "in some embodiments, alkyl is substituted. In some embodiments, the alkyl group is unsubstituted. The expression "the photoluminescent composite can increase the contrast" should be interpreted, for example, as "in some embodiments, the photoluminescent composite of the invention does increase the contrast. In some embodiments, the photoluminescent complexes of the present invention do not improve contrast. The expression "the color conversion film may further comprise a second photoluminescent compound" should be interpreted, for example, as "in some embodiments, the color conversion film will further comprise a second photoluminescent compound. In some embodiments, the color conversion film will not further include a second photoluminescent compound. "

As used herein, when a compound or chemical structure is referred to as "substituted," it includes more than one substituent. 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 more than one substituent on the parent group structure. In one or more forms, the substituents may be independently selected from optionally substituted alkyl or alkenyl, or C ₃ -C ₇ A heteroalkyl group.

The term "alkyl" as used herein refers to a hydrocarbon group having no double or triple bonds. An "alkene moiety" refers to a group having at least one carbon-carbon double bond, and an "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 may have 1 to 6 carbon atoms (regardless of where it appears herein, numerical ranges such as "1 to 6" refer to each integer within 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 the present definition also encompasses the occurrence of the term "alkyl" where no numerical range is specified. The alkyl group of the compounds specified herein may be designated "C ₁ -C ₆ Alkyl "or similar names. By way of example only, "C ₁ -C ₆ Alkyl "means that there are from one to six carbon atoms in the alkyl chain, i.e., the alkyl chain is selected from methyl, ethyl, propyl, isopropyl, n-butyl, n-,Isobutyl, sec-butyl and tert-butyl. Thus, C ₁ -C ₆ The alkyl group comprising C ₁ -C ₂ Alkyl radical, C ₁ -C ₃ Alkyl radical, C ₁ -C ₄ Alkyl radical, C ₁ -C ₅ An alkyl group. Alkyl groups may be substituted or unsubstituted. Typical alkyl groups include, but are in no way limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, ethenyl, propenyl, butenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.

The term "heteroalkyl," as used herein, refers to an alkyl group, as defined herein, in which more than one constituent carbon atom has been replaced with a heteroatom. An example of heteroalkyl is "alkoxy," which 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 having a delocalized pi-electron system containing 4n +2 pi electrons, where n is an integer. Aromatic rings may be formed, for example, from five, six, seven, eight, nine, or more than nine atoms. The aromatic may be optionally substituted. The term "aromatic" includes both carbocyclic aryl (e.g., phenyl) and heterocyclic aryl (or "heteroaryl" or "heteroaromatic") groups (e.g., pyridine). The term includes monocyclic or fused-ring polycyclic (i.e., rings that share adjacent pairs of carbon atoms) groups.

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. The monocyclic hydrocarbon ring includes a group having 3 to 12 carbon atoms. Illustrative examples of monocyclic groups include the following moieties:

and the like. Illustrative examples of polycyclic groups include the following moieties:

[ bicyclo octane]、

[ Dicyclopentane ]]、

[ bicycloheptane]、

[ bicycloheptane]、

[ bicyclodecane]、

[ decahydronaphthalene ]]、

[ octahydropentalene ] A process for preparing a compound]、

Octahydroindene,

[ hexahydroindene ] hexahydro]、

[1,2,3, 4-tetrahydronaphthalene]、

[1,2,3,3 a-tetrahydropentalene]、

[ 9H-fluorene ]]And, and

spiro [ cyclopentane-1, 9' -fluorene]And the like.

The term "aryl" as used herein means an aromatic ring in which the atoms forming the ring are each carbon atoms. The aryl group may be substituted or unsubstituted. Examples of aryl groups include, but are not limited to, phenyl, naphthyl, phenanthryl, tetracenyl, fluorenyl, pyrenyl, and the like.

The term "heteroaryl" refers to an aryl group comprising one or more ring heteroatoms selected from nitrogen, oxygen and sulfur, wherein the heteroaryl group has from 4 to 10 atoms in its ring system. It is understood that the heteroaryl ring may have additional heteroatoms in the ring. In the heteroaryl group having two or more heteroatoms, these two or more heteroatoms may be the same as or different from each other. Heteroaryl groups may be optionally substituted. An N-containing heteroaryl moiety refers to an aryl group in which at least one of the backbone atoms of the ring is a nitrogen atom. Illustrative examples of heteroaryl groups include the following moieties: pyrrole, imidazole, and the like.

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

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

The term "moiety" as used herein refers to a particular segment or functional group of a molecule. Chemical moieties are generally considered to be chemical entities embedded or attached to a molecule.

The term "cyano" or "nitrile" as used herein refers to any organic compound that contains 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 through a ring carbon), and heteroalicyclic (bonded through a ring carbon). Any of the hydroxyl or carboxyl side chains on the compounds described herein can be esterified. Procedures and specific groups for preparing such esters are known to those skilled in the art and can be readily found in the references.

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

The term "ketone" as used herein refers to a chemical moiety comprising a carbonyl group (C ═ O) attached to two alkyl or aryl groups, wherein the general formula is RC (═ O) R', wherein the terms alkyl and aryl are as defined herein.

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

BODIPY may be formed from a disubstituted boron atom (usually BF) ₂ Unit) of a composite dipyrromethene group. The IUPAC name for the general core structure of BODIPY is 4, 4-difluoro-4-bora-3 a,4 a-diaza-s-indacene.

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

the present invention includes a photoluminescent composition that absorbs light energy at a first wavelength and emits light energy at a second, higher wavelength. The photoluminescent complexes of the present invention may comprise a donor chromophore, wherein the donor chromophore may absorb blue light (400-480 nm wavelength) and release excitation energy in response thereto; an acceptor chromophore, which may include a dipyrromethene Boron (BODIPY) derivative that may absorb excitation energy released by the donor chromophore, wherein the acceptor chromophore may subsequently emit light at a second wavelength, which may be a higher wavelength light than blue; and a linker complex that can link together the donor chromophore and the acceptor chromophore. The photoluminescent compounds described herein can be incorporated into color conversion films to significantly improve the resolution between colors in the red, green, and blue (RGB) gamut, resulting in improved contrast and higher quality color reproduction.

At one endIn some embodiments, the photoluminescent complex includes a donor chromophore, an acceptor chromophore, and a linker complex. The donor chromophore and the acceptor chromophore are linked to create a spatial relationship with the linker complex. In some embodiments, the donor chromophore can absorb light within the blue wavelengths and then release excitation energy. The acceptor chromophore may absorb the excitation energy released by the donor chromophore, and the acceptor chromophore may then emit light at a second wavelength, where the light at the second wavelength may be light at 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 is via fluorescence resonance energy transfer (

Stress energy transfer) (FRET) occurs.

The photoluminescent complex can be represented by formula I: a- (L-D) _1-3 By representation, it is meant that 1,2, or 3L-D groups can be attached to the acceptor chromophore a, as shown in formulas IA, IB, and IC below:

wherein a is an acceptor chromophore, L is a linker complex, and D is a donor chromophore.

In some embodiments, the donor chromophore (D) may include a perylene derivative of the formula;

in some embodiments, R ⁸ 、R ¹⁰ And R ¹¹ Can be hydrogen (H) or trifluoromethyl (CF) ₃ ). 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 embodimentsIn the scheme, 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 Is H. In some embodiments, R ⁸ 、R ¹⁰ And R ¹¹ Is CF ₃ 。

Some embodiments include a photoluminescent composite, wherein the photoluminescent composite includes a donor chromophore that absorbs light within blue wavelengths. In some embodiments, the maximum blue light absorbance of the donor chromophore may be in the range of from 400nm to about 480nm, from about 400nm to about 410nm, from about 410nm to about 420nm, from about 420nm to about 430nm, from about 430nm to about 440nm, from about 440nm to about 450nm, from about 450nm to about 460nm, from about 460nm to about 470nm, from about 470nm to about 480nm, or any wavelength limited by these ranges. In some embodiments, the maximum absorbance peak of the photoluminescent complex can be about 450 nm. In other embodiments, the maximum absorbance peak of the donor chromophore can be about 405 nm. In further embodiments, the maximum absorbance peak of the donor chromophore can be about 480 nm.

In some embodiments, the acceptor chromophore (a) may include a dipyrromethene Boron (BODIPY) derivative. BODIPY derivatives may be of the general formula:

with respect to any related structural representation, as shown in formula III, each R' is H, methyl (-CH) ₃ ) F, or CF ₃ . In some embodiments, one R' is H. In some embodiments, both R' are H. In some embodiments, one R' is CH ₃ . In some embodiments, two R' are CH ₃ 。

With respect to any related structural representation, such as formula III, R "is — H, or a bond to L-D, wherein L is a linking group and D is a donor chromophore.

With respect to any relevant structural representation, formulaIII，R ¹ And R ² Independently is 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, R ¹ And R ² Are all H. In some embodiments, R ¹ And R ² Are all CH ₃ 。

With respect to any relevant structural representation, formula III, R ³ And R ⁴ Independently H, F, Br, or-CF ₃ Optionally with 1 or 2-CH ₃ 、-F、-CF ₃ A substituted phenyl group, or a group L-D, wherein L is a linking group and D is a 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-L-D. In some embodiments, R ³ And R ⁴ Is H. In some embodiments, R ³ And R ⁴ Is F. In some embodiments, R ³ And R ⁴ Is phenyl, such as unsubstituted phenyl. In some embodiments, R ³ And R ⁴ Is phenyl substituted with-L-D.

With respect to any related structural representation, such as formula III, X is a bridging group connecting the phenyl aryl ring and the pyrrole ring, e.g. alkyl, including-C _x H _2x -, where x is 1,2,3,4, etc., e.g., -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; or an aromatic spiro ring-polycyclic radical, wherein R ^a Is C ₁ -C ₄ And wherein Ar is aryl or heteroaryl. 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, where X is spiro-cycloalkyl, the spiro-cycloalkyl may include spiro-cyclopentane.

In some embodiments, the BODIPY moiety or a may be:

in some embodiments, the photoluminescent complex comprises a linker complex or L, wherein the linker complex covalently links the blue light absorbing moiety (a) to the BODIPY emitting moiety (D). In some embodiments, the linker complex may comprise a single bond between the blue light absorbing moiety and the BODIPY moiety. In other embodiments, the linking group complex may include a substituted or unsubstituted ester group. In some embodiments, the photoluminescent complex emits red light.

With respect to any related structural representation, such as formula I, formula IA, formula IB, or formula IC, L is a linker complex comprising an optionally substituted C ₂ -C ₇ Esters or C ₃ -C ₅ A ketoester. In some embodiments, L is:

it is believed that the ester linking group helps to increase the distance between the blue light absorbing moiety and the BODIPY moiety, thereby creating a through space energy transfer (FRET), rather than a through bond energy transfer (trogh bond energy transfer), resulting in a quantum yield of the photoluminescent composite of greater than 70%.

In one embodiment, the photoluminescent complexes can have high emission quantum yields. In some embodiments, the emission quantum yield may be greater than 50%, 60%, 70%, 80%, or 90%; and may be up to or near 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 may be up to or near 100%. In some embodiments, the emission quantum yield may be greater than 80%, and may be up to 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 emissive quantum yield of the absorbing light-emitting moiety may be greater than 75% and may be as high as 100%. In some embodiments, the quantum yield may 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 may be up to or near 1 (100%). Quantum yield measurements in membranes can be performed by spectrophotometers, for example Quantaurus-QY spectrophotometers (Humamatsu, inc., Campbell, CA, USA).

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

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

The photoluminescent compositions of the present invention can have tunable emission wavelengths. By substituting the BODIPY moiety of the acceptor chromophore with different substituents, the emission wavelength can be tuned between 575nm and about 650nm or any number limited by this range.

In some embodiments, the maximum peak absorption of the donor chromophore can be between about 400nm and about 480nm wavelength. In some embodiments, the peak absorption may be between about 400nm to about 405nm, about 405nm to about 410nm, about 410nm to about 415nm, about 415nm to about 420nm, about 420nm to about 425nm, about 425nm to about 430nm, about 430nm to about 435nm, about 435nm to about 440nm, about 440nm to about 445nm, about 445nm to about 450nm, about 450nm to about 455nm, about 455nm to about 460nm, about 460nm to about 465nm, about 465nm to about 470nm, about 470nm to about 480nm, and any number limited by these ranges.

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

Other embodiments include photoluminescent complexes in which the spatial distance of the donor chromophore and the acceptor chromophore is optimized by a linker complex to transfer the emission energy of the blue light absorbing moiety to the BODIPY derivative light emitting moiety.

In some embodiments, the blue light absorbing moiety can be a perylene derivative of formula I:

with respect to the perylene derivatives of formula II, the perylene may comprise perylene, wherein R is ⁸ 、R ¹⁰ And R ¹¹ May be selected from hydrogen (H) or trifluoromethyl (CF) ₃ ). In some embodiments, R ⁹ Is H.

The photostability (or durability) of organic compounds and composites is a very common problem. The photostability of organic photoluminescent composites is mainly due to the photo-oxidation process. It is believed that the addition of an electron withdrawing group (also referred to as an electron accepting group) to the reactive site on the perylene structure attracts electrons from the atomic groups on the photoluminescent composite through an induction effect or a resonance effect, resulting in a lower HOMO/LUMO energy level, which is detrimental to the photooxidation of the photoluminescent composite.

The electron accepting group may include a cyano group (-CN), a fluorine-containing alkyl group such as trifluoromethyl group (-CF3), or a fluorine-containing aryl group such as 4- (trifluoromethyl) phenyl group, because these groups are less susceptible to chemical decomposition.

In some embodiments, the perylene derivative can be linked to a second dipyrromethene Boron (BODIPY) derivative acceptor luminescent moiety. In some embodiments, the linker complex and the second absorbing luminescent complex may be covalently bonded to formula I.

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

in some embodiments, the photoluminescent composition comprises the structure shown below.

Some embodiments include a color conversion film comprising a transparent substrate layer and a color conversion layer, wherein the color conversion layer comprises a resin matrix and at least one photoluminescent composite, wherein the at least one photoluminescent composite comprises the photoluminescent composite described above dispersed within the resin matrix. In some embodiments, the color conversion film may be described as including more than one photoluminescent complex described herein. In some embodiments, the color conversion film may include a photoluminescent complex that absorbs in the light wavelength range of 400nm to 480nm and emits in the light wavelength range of 510nm to 560 nm. In some embodiments, the color conversion film may include a photoluminescent composition that absorbs in the light wavelength range of 400nm to 480nm and emits in the light wavelength range of 575nm to 650 nm.

In some embodiments, the color conversion film may include a transparent substrate layer. The transparent substrate layer has two opposing surfaces, wherein the color conversion layer may be disposed on and in physical contact with a surface of the transparent layer that is to be adjacent to the light emitting source. The transparent substrate is not particularly limited, and those skilled in the art can select from transparent substrates used in the art. Some non-limiting examples of transparent substrates include PE (polyethylene), PP (polypropylene), PEN (polyethylene naphthalate), PC (polycarbonate), PMA (polymethyl acrylate), PMMA (polymethyl methacrylate), CAB (cellulose acetate butyrate), PVC (polyvinyl chloride), PET (polyethylene terephthalate), PETG (glycol modified polyethylene terephthalate), PDMS (polydimethylsiloxane), COC (cyclic olefin copolymer), PGA (polyglycolide or polyglycolic acid), PLA (polylactic acid), PCL (polycaprolactone), PEA (polyethylene adipate), PHA (polyhydroxyalkanoate), PHBV (poly (3-hydroxybutyrate-co-3 hydroxyvalerate)), PBE (polybutylene terephthalate), and PTT (polytrimethylene terephthalate). Any of the above resins may be the corresponding/respective monomer and/or polymer.

In some embodiments, the transparent substrate may have two opposing surfaces. In some embodiments, the color conversion film may be disposed on and in physical contact with one of the opposing surfaces. In some embodiments, the side of the transparent substrate on which the color conversion film is not disposed may be adjacent to the light source. The substrate may function as a support during the preparation of the color conversion film. The kind of the substrate used is not particularly limited, and the material and/or thickness is not limited as long as it is transparent and can function as a support. One skilled in the art can determine which material and thickness to use as a support 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 those described herein) dissolved with a solvent.

The resin matrix forms a continuous phase and may include materials having superior processability, heat resistance, and transparency. The resin matrix material may comprise a polymer. Some non-limiting examples of polymers for color conversion films include, but are not limited to, poly (meth) acrylic based materials, such as Polymethylmethacrylate (PMMA), Polycarbonate (PC) based materials, Polystyrene (PS) based materials, Polyarylene (PAR) based materials, polyurethane based materials, styrene-acrylonitrile (SAN) based materials, and polyvinylidene fluoride (PVDF) based materials, among others. The resin matrix is not limited and one skilled in the art will be able to select which polymeric material to use for its application.

Solvents that may be used to dissolve or disperse the compound and resin may include alkanes such as butane, pentane, hexane, heptane, and octane; cycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane; alcohols, such as ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, decanol, undecanol, diacetone alcohol, furfuryl alcohol; cellosolves ^TM Such as methyl Cellosolve ^TM Ethyl Cellosolve ^TM Butyl Cellosolve ^TM Methyl Cellosolve ^TM Acetate, and ethyl Cellosolve ^TM Acetate ester; propylene glycols and their derivatives, such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, and dipropylene glycol dimethyl ether; ketones, such as acetone, methyl amyl ketone, cyclohexanone, acetophenone; ethers such as dioxane and tetrahydrofuran; esters such as butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, diethyl oxalate, ethyl pyruvate, ethyl 2-hydroxybutyrate, ethyl acetoacetate, methyl lactate, ethyl lactate and methyl 3-methoxypropionate; halogenated hydrocarbons such as chloroform, 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 further comprise a second photoluminescent complex, wherein the second complex has an absorbance of emission within a wavelength of 400nm to 470nm and within a wavelength of 510nm to 560 nm. In some embodiments, the color conversion film may further include a photoluminescent complex that absorbs in the light wavelength range of 400nm to 480nm and emits in the light wavelength range of 575nm to 650 nm.

In some embodiments, the color conversion film further comprises an additive. The additive may be used to prevent deterioration of the photoluminescent compound and improve durability, i.e., inhibit decrease in light emission intensity with time. In some embodiments, LA-57 is an effective additive.

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

Singlet oxygen is known to be generated as a result of electron and energy exchange between the perylene or BODIPY structure and the ground-state oxygen molecule. In the color conversion film of the present invention, the photoluminescent compound is excited by the excitation light and emits light of a different wavelength than the excitation light, thereby converting light of one wavelength to a second, higher wavelength. With each cycle of excitation light emission, the probability of singlet oxygen generation increases due to the interaction between the generated excited species and the oxygen molecules present in the composition. The probability of collision of the photoluminescent compound with singlet oxygen species increases, leading to degradation of the photoluminescent compound. Some non-limiting examples of singlet oxygen quenchers include nickel additives, such as nickel chloride, nickel (II) bis (acetylacetonate) (Ni (acac) ₂ Millipore Sigma, Burlington, MA USA), nickel carbonate, etc.

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

In some embodiments, the additive may include a hindered light stabilizer. The hindered light stabilizer may include a tertiary amine. Some non-limiting examples of tertiary amines include tetrakis (2,2,6, 6-tetra-methyl-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-diethylaniline, 1,2,2,6, 6-pentamethylpiperidine, bis (1,2,2,6, 6-pentamethyl-4-piperidinyl) sebacate, and the like.

The color conversion film may be about 1 μm to about 200 μm thick. In some embodiments, the color conversion film has a thickness of 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, 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 limited by the foregoing range.

In some embodiments, the color conversion film may absorb light in the wavelength range of 400nm to about 480nm, and may emit light in the range of about 575nm to about 650 nm. In some embodiments, the color conversion film may absorb light in the wavelength range of 400nm to 480nm and may emit light in the range of 510nm to about 560 nm. In further embodiments, the color conversion film may absorb light in the range of 400nm to about 480nm and may emit light at two higher wavelengths, a wavelength range of 510nm to about 560nm and a wavelength range of 575nm to about 650nm, or any combination thereof.

Some embodiments include a method of making a color conversion film, the method comprising: dissolving a resin matrix and at least one photoluminescent complex in a solvent, wherein the at least one photoluminescent complex is as described above; and applying the mixture to a surface of a transparent substrate.

In some embodiments, the method of making a color conversion film further comprises dissolving a second photoluminescent complex having an excitation wavelength of 400nm to about 480nm and an emission wavelength of 510nm to about 560 nm. In some embodiments, the second photoluminescent complex has an excitation wavelength of 400nm to about 480nm and an emission wavelength of 575nm to about 560 nm.

In some embodiments, the method further comprises dissolving the 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 further comprises 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 having high light stability. In some examples, the absorption at the peak absorption wavelength is measured before and after the color conversion film is exposed to the LED light for 165 hours, 330 hours, and 500 hours, respectively, as measured by UV-vis 3600(Shimadzu), and dividing the remaining absorption (measured after each exposure time) by the absorption before exposure is indicative of the light stability of the color conversion film. In some embodiments, the photostability is at least 80%, at least 82%, at least 85%, at least 90%, or at least 93%, and can approach 100% after 165 hours of exposure. In other embodiments, the photostability 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 that may include a backlight unit as described herein.

Unless otherwise indicated, all numbers expressing quantities of ingredients, properties (e.g., molecular weights), reaction conditions, and so forth, used in the specification and embodiments are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the specification and attached embodiments are approximations that may vary depending upon the desired properties sought to be obtained. And are not intended to limit the application of the doctrine of equivalents in any way. To the extent of the embodiments, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

For the disclosed processes and/or methods, the functions performed in the processes and methods may be performed in a different order, as the context dictates. Further, the outlined steps and operations are only provided as examples, and some of the steps and operations may be optional, combined into fewer steps and operations, or expanded into additional steps and operations.

The invention may sometimes be said to consist in or consist in different parts or in connection with different other parts. Such depicted architectures are merely exemplary, and many other architectures can be implemented which achieve the same or similar functionality.

Detailed description of the preferred embodiments

Embodiment 1. a photoluminescent composition comprising:

a donor chromophore, wherein the donor chromophore absorbs light within a blue wavelength and emits excitation energy in response thereto, wherein the donor chromophore comprises a perylene derivative of the formula;

wherein R is ⁸ 、R ¹⁰ And R ¹¹ Selected from H or CF ₃ And wherein R ⁹ Is H;

an acceptor chromophore comprising a dipyrromethene Boron (BODIPY) derivative, wherein the acceptor chromophore absorbs the excitation energy emitted by the donor chromophore, wherein the acceptor chromophore subsequently emits light at a second wavelength that is a higher wavelength light than blue wavelengths; and

a linker complex for linking the donor chromophore and the acceptor chromophore; and wherein the photoluminescent composite has an emission quantum yield greater than 80%.

Embodiment 2. the photoluminescent complex according to embodiment 1, wherein the BODIPY derivative is of the general formula:

wherein R' is independently H, methyl (-CH) ₃ ) F, or CF ₃ ；

R' is-H, or a bond to L-D;

R ¹ and R ² Independently selected from H or methyl (-CH) ₃ )；

R ³ And R ⁴ Independently H, F, Br, -CF ₃ Optionally with 1 or 2-CH ₃ 、-F、-CF ₃ Substituted phenyl, or-L-D groups;

x is a bridging group connecting the phenyl aryl 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 -, spiro-cycloalkyl, or aromatic spiro-polycyclic group, in which R ^a Is C ₁ -C ₄ And wherein Ar is aryl or heteroaryl;

l is a linker complex comprising an optionally substituted C ₄ -C ₇ Esters or C ₃ -C ₅ Ketoacid esters; and D is a donor chromophore.

Embodiment 3. a photoluminescent complex according to embodiment 1, wherein when X forms a spiro-cycloalkyl, the spiro-cycloalkyl is spiro-cyclopentane.

Embodiment 4. a photoluminescent complex according to embodiment 1, wherein when X forms a spiro-polycyclic group, the spiro-polycyclic group is spiro-fluorene.

Embodiment 5. photoluminescent complexes according to embodiments 1,2,3 and 4, wherein C is ₄ -C ₇ The ester linking group is of the general formula:

embodiment 6. photoluminescent complexes according to embodiments 1,2,3 and 4, wherein C is ₃ -C ₅ The ketoester linking group is of the general formula:

embodiment 7. a photoluminescent complex according to embodiments 1,2,3,4, 5 and 6, wherein the photoluminescent complex is selected from one of the following structures:

embodiment 8. a color conversion film, comprising:

a transparent substrate layer;

a color conversion layer, wherein the color conversion layer comprises a resin matrix, and

at least one photoluminescent complex, wherein the at least one photoluminescent compound comprises a photoluminescent compound according to embodiments 1,2,3,4, 5,6 and 7 dispersed in the resin matrix.

Embodiment 9. the color conversion film according to embodiment 8, further comprising a singlet oxygen quencher.

Embodiment 10. the color conversion film according to embodiment 8, further comprising a free radical scavenger.

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

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

Embodiment 13. the color conversion film according to embodiment 8, further comprising a photoluminescent complex having an absorbance within a wavelength of 400nm to 480nm and an emission within a wavelength of 510nm to 560 nm.

Embodiment 14. a method of making a color conversion film according to embodiments 8,9, 10, 11,12, and 13, the method comprising:

dissolving a resin matrix and at least one photoluminescent complex in a solvent, wherein the at least one photoluminescent complex is described in embodiments 1,2,3,4, 5,6, and 7; and is

The mixture is applied to a transparent substrate surface.

Embodiment 15. the method according to embodiment 14, further comprising dissolving a photoluminescent complex having an absorbance in the range of 400nm to 480nm and an emission in the wavelength range of 510nm to 560 nm.

Embodiment 16. the method according to embodiment 14, further comprising dissolving the radical scavenger in a solvent.

Embodiment 17. the method according to embodiment 14, further comprising dissolving the singlet oxygen quencher in a solvent.

Embodiment 18. a backlight unit comprising the color conversion film according to embodiment 8.

Embodiment 19. a display device comprising the backlight unit according to embodiment 18.

Examples

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

Example 1 comparative example 1 (CE-1):

CE-1: 0.75g of 4-hydroxy-2, 6-dimethylbenzaldehyde (5mmol) and 1.04g of 2, 4-dimethylpyrrole (11mmol) are dissolvedThe solution was dissolved in 100mL of anhydrous dichloromethane. The solution was degassed for 30 minutes. Then, one drop of trifluoroacetic acid was added. The solution was stirred at room temperature under an argon atmosphere overnight. The next day the solution was filtered and then washed with dichloromethane to give dipyrromethane. Next, 1.0g of dipyrromethane was dissolved in 60mL of TNF. 5mL of trimethylamine was added to the solution, which was then degassed for 10 minutes. After degassing, 5mL of trifluoroboron-diethyl ether was slowly added followed by heating at 70 ℃ for 30 minutes. The resulting solution was loaded onto silica gel and purified by flash chromatography using dichloromethane as eluent. The desired fractions were collected and dried under reduced pressure to give 0.9g of an orange solid (76% yield). LCMS (APCI +): c ₂₁ H ₂₄ BF ₂ N ₂ Calculated O (M + H) 369; measured value: 369. ¹ h NMR (400MHz, 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): which is Wakamiya, Atsushi et al, Chemistry Letters, 37(10), 1094-; 2008 for the Synthesis

Example 2. synthesis of photoluminescent complexes:

example 2.1: RLE-1

Compound 1(4, 5-dihydro-1H-benzo [ g)]Indole): a mixture of DMSO (50mL), KOH (3.36g), and NH2OH.HCl (4.17g) was stirred at room temperature for 30 minutes, then 1-tetralone (7.3g) in DMSO (25mL) was added. The mixture was stirred at 70 ℃ for another 30 minutes. KOH (8.41g) was then added and the resulting mixture was heated to 140 ℃ and a solution of 1, 2-dichloroethane (9.9g) in DMSO (25mL) was added dropwise over 4 hours. After cooling to room temperature, the solution was poured into 200mL of saturated NH ₄ Cl solution, and the solution was extracted with ethyl acetate (200 mL. times.3). The organic phase was collected and washed with Na ₂ SO4 was dried, concentrated to 10mL, and then diluted with 10mL of dichloromethane and 50mL of hexane. Using dichloro-chlorineThe solution was subjected to flash chromatography (silica gel) with eluent of methane/hexane (0% → 30%) and a second major fraction was collected. After removal of the solvent under reduced pressure, a pale yellow solid was obtained as the desired product (3.5g, 41% yield). LCMS (APCI +): c ₁₂ H ₁₂ Calculated value of N (M + H): 170; measured value 170.

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

compound 1.2: to a solution of compound 1.1(200mg, 0.42mmol) in 20mL of dichloromethane was added tetrachlorop-benzoquinone (100mg, 0.45mmol) at 0 ℃ with cooling in an ice-water bath. The mixture was stirred for 20 minutes. Then, to the resulting mixture was added 0.5mL of trimethylamine, followed by 0.8mL of BF ₃ -an ether. The whole was stirred at room temperature overnight, then loaded on silica gel and purified by flash chromatography using an eluent of dichloromethane/hexane (0% → 80%). The desired red luminescent fractions were collected. After removal of the solvent, a metallic dark red solid was obtained (150mg, 72% yield). LCMS (APCI +): c ₃₃ H ₂₈ BF ₂ N ₂ Calculated O (M + H): 517; measured value: 517.

compound 1.3 (5-oxo-5- (peren-3-yl) pentanoic acid): the stir bar was charged to a 3L 2-neck round bottom flask and flushed thoroughly with argon. Mixing AlCl ₃ (34.7mmol, 4.624g) was added to the flask followed by addition of anhydrous dichloromethane (600 mL). The reaction mixture was cooled to 0 ℃ with an ice water bath and methyl 5-chloro-5-oxopentanoate (30.4mmol, 5.00g) was added via syringe under argon with stirring. The mixture was stirred at 0 ℃ for one hour, then perylene (28.9mmol, 7.300g) was added with stirring. The cooling bath was removed and the reaction mixture was placed in the chamberStir at room temperature for two hours. The flask was fitted with a finned air condenser and heated in a heating block set at 45 ℃ and stirred under argon overnight. The reaction mixture was cooled to room temperature and quenched by the addition of crushed ice (600mL, loose fill). To the mixture was added 6N aqueous HCl (100 mL). Stirring was continued until all the ice had melted. The layers were separated and the aqueous layer was extracted with DCM (2X 200 mL). The combined organic layers were washed with MgSO ₄ Dried, filtered, and concentrated in vacuo. The crude reaction was purified by flash chromatography on silica gel (100% DCM (3CV) → 5% EtOAc/DCM (10 CV)). The product containing fractions were collected and concentrated in vacuo to yield 3.810g, 35% yield. Ms (apci): c ₂₆ H ₂₀ O ₃ The calculated value of (M + H) is 381; measured value: 381.

next, a stir bar was charged to a 250mL 2-neck round bottom flask and flushed with argon. To the flask was added methyl 5-oxo-5- (perylene-3-yl) valerate (3.00mmol, 1.141g) and KOH (30.0mmol, 1.683g), followed by ethanol (200 proof, 200 mL). The flask was fitted with a finned air condenser and heated in a 95 ℃ heating block and stirred under argon for two hours. The reaction mixture was cooled to room temperature and diluted with water in an erlenmeyer flask (to a total volume of 500mL) and quenched with 6N aqueous HCl (5 mL). The resulting precipitate was collected and concentrated in vacuo to yield 1.013g (92% yield). Ms (apci): c ₂₅ H ₁₈ O ₃ Calculated value of (M-H) 365; measured value: 365.

RLE-1: to the compound 1.2(52mg, 0.1mmol), the perylene compound 1.3[ 5-oxo-5-9-perylen-3-yl) pentanoic acid]To a solution of (48mg, 0.13mmol), DMAP (25mg, 0.2mmol) and p-TsOH (34mg, 0.18mmol) in dichloromethane (7mL) was added a solution of DIC (63mg, 0.5mmol) in 1mL dichloromethane. The whole was stirred at room temperature overnight and then purified by flash chromatography (silica gel) using an eluent of dichloromethane/hexane (0% → 80%). The desired fractions were collected and, after removal of the solvent, a dark green solid was obtained (70mg, 81% yield). LCMS (APCI +): c ₅₈ H ₄₄ BF ₂ N ₂ O ₃ Calculated value of (M + H): 865; measured value: 865. ¹ H NMR(400MHz，dichloromethane-d ₂ )δ8.66(d，J＝8.0Hz，2H)，8.50(d，J＝8.6Hz，1H)，8.25–8.16(m，4H)，7.89(d，J＝8.0Hz，1H)，7.69(dd，J＝17.5，8.1Hz，2H)，7.54(dd，J＝8.6，7.6Hz，1H)，7.46(td，J＝7.8，2.5Hz，2H)，7.36(td，J＝7.6，1.7Hz，2H)，7.27–7.18(m，4H)，6.86(s，2H)，6.27(s，2H)，3.17(t，J＝7.1Hz，2H)，2.83(dd，J＝8.3，5.9Hz，4H)，2.70(t，J＝7.3Hz，2H)，2.57(dd，J＝8.3，5.8Hz，4H)，2.20(q，J＝7.2Hz，2H)，2.14(s，6H)。

Example 2.2 RLE 2:

RLE-2: to a solution of compound 1.2(52mg, 0.1mmol), 4- (peren-3-yl) butyric acid (44mg, 0.13mmol), DMAP (25mg, 0.2mmol), p-TsOH (34mg, 0.18mmol) in dichloromethane (7mL) was added a solution of DIC (63mg, 0.5mmol) in 1mL dichloromethane. The whole was stirred at room temperature overnight and then purified by flash chromatography (silica gel) using an eluent of dichloromethane/hexane (0% → 70%). The desired fractions were collected and, after removal of the solvent, a dark green solid was obtained (80mg, 95.6% yield). LCMS (APCI +): c ₅₇ H ₄₄ BF ₂ N ₂ O ₂ Calculated value of (M + H): 837, adding a solvent; measured value: 837. ¹ h NMR (400MHz, dichloromethane-d) ₂ )δ8.79(d，J＝8.0Hz，2H)，8.34–8.20(m，4H)，8.04(d，J＝8.4Hz，1H)，7.74(dd，J＝8.2，4.9Hz，2H)，7.66–7.45(m，6H)，7.40(dd，J＝7.4，1.2Hz，1H)，7.38–7.31(m，3H)，6.94(s，2H)，6.39(s，2H)，3.24(dd，J＝8.6，6.7Hz，2H)，2.96(dd，J＝8.3，5.9Hz，4H)，2.78(t，J＝7.2Hz，2H)，2.70(dd，J＝8.3，5.9Hz，4H)，2.30(dt，J＝9.1，7.2Hz，2H)，2.24(s，6H)。

Example 2.3 RLE-3:

compound 3.1 (8-bromo-4, 5-dihydro-1H-benzo [ g)]Indole): a250 mL 2-neck round bottom flask was equipped with a finned condenser, stir bar, and gas connectors. The flask was flushed with argon and KOH (85% purity, 60.0mmol, 4.106g) and NH were added ₂ OH.HCl (60.0mmol, 4.169g) was added to the flask followed immediately by anhydrous DMSO (5 mL). The mixture was stirred at room temperature under argon for 5 minutes, then 7-bromo-3, 4-dihydronaphthalen-1 (2H) -one (50.0mmol, 11.255g) was added. The flask was stoppered and stirred at room temperature for 1 minute, then heated to 110 ℃ in a heating block for 1 hour. More KOH (85% purity, 300mmol, 16.833g) was added to the flask and the temperature of the heating block was raised to 140 ℃. Anhydrous dichloroethane (200mmol, 15.8mL) was diluted with anhydrous DMSO to a total volume of 40 mL. This solution was transferred to a 50mL syringe and added to the reaction mixture over a period of 30 minutes at 140 ℃ with very vigorous stirring. More dichloroethane/DMSO solution was prepared and another 10mL of this mixture was added by syringe pump over another 30 minutes. The reaction mixture was cooled to 0 ℃ in an ice-water bath and quenched with saturated aqueous ammonium chloride (100 mL). The mixture was diluted with water (400mL) and extracted with ether (250mL) 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 (2X 200 mL). The combined organic layers were washed with water (5X 50mL), brine (50mL), and MgSO ₄ Dried, filtered and evaporated to dryness. The crude mixture was purified by flash chromatography on silica gel (100% hexane (1CV) → 10% DCM/hexane (1CV) → 30% DCM/hexane (9 CV)). The product fractions were repurified on silica gel (100% hexane (1CV) → 1% EtOAc/hexane 0CV) → 10% EtOAc/hexane (9 CV)). The product fractions were collected and rotary evaporated to give 4.507g, 36% yield. The major impurities include the N-vinyl product and two O-linked, ethylene-bridged oximes. Ms (apci): c ₁₂ H ₁₀ The calculated value of BrN (M + H) is 248; measured value: 248.

compound 3.2((T-4) - [2- [ (4, 5-dihydro-8-bromo-2H-benzo [ g)]Indol-2-ylidene-kappa N) - (3, 5-dimethyl-4-hydroxyphenyl) methyl]-4, 5-bishydro-1H-benzo [ g]Indolo-kappa N]Difluoro boron): a250 mL 2-neck round bottom flask was equipped with a gas connector and a stir bar. The flask was flushed with argon, and compound 3.1(5.21mmol, 1.293g) and 4-hydroxy-2, 6-dimethylbenzaldehyde (2.66mmol, 399mg) were added to the flask, followed by the addition of anhydrous dichloroethane (50 mL). The reaction mixture was sparged with argon for 30 minutes, then TFA (0.1% v/v, 50. mu.L) was added via syringe. The reaction mixture was sparged with argon for an additional 15 minutes, 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 in a heating block at 50 ℃ and stirred for 24 hours. The reaction was cooled to 0 ℃ in an ice-water bath and tetrachlorop-benzoquinone (2.61mmol, 641mg) was added with stirring. The reaction was stirred at 0 ℃ for 20 minutes at which time the oxidation was complete. Addition of BF to the reaction ₃ .OEt ₂ (58.4mmol, 7.2mL) and triethylamine (34.9mmol, 4.9mL), and the mixture was stirred at 0 ℃ for 30 minutes, then the ice-water bath was removed and the reaction was stirred at room temperature for three days. The reaction was then heated to 60 ℃ in a heating block for 6 hours. The reaction mixture was evaporated to dryness and purified by flash chromatography on silica gel (100% hexane (1CV) → 10% EtOAc/hexane (0CV) → 50% EtOAc/hexane (8CV) → 60% EtOAc/hexane (0CV) → 60% EtOAc/hexane (2 CV)). Most of the product eluted as pure, some co-eluted with impurities. Impure fractions were collected, evaporated, and re-purified by flash chromatography on silica gel (100% hexane (2CV) → 20% EtOAc/hexane (0CV) → 50% EtOAc/hexane (10 CV)). The pure fractions from both columns were combined and evaporated to dryness to give the product, 1170mg, 67% yield. Ms (apci): c ₃₃ H ₂₅ BBr ₂ F ₂ N ₂ O(M ^- ) 672; measured value: 672. ¹ h NMR (400MHz, chloroform-d) δ 9.01(d, J ═ 2.0Hz, 2H), 7.43(dd, J ═ 8.1, 2.0Hz, 2H), 7.12(d, J ═ 8.1Hz, 2H), 6.63(s, 2H), 6.34(s, 2H), 2.85(dd, J ═ 8.3, 5.9Hz, 4H), 2.65(dd, J ═ 8.4, 5.8Hz, 4H), 2.17(s, 6H).

RLE-3((T-4) - [2- [ (4, 5-dihydro-8-bromo-2H-benzo [ g))]indol-2-ylidene-N) - (3, 5-dimethyl-4- (N-methyl-4-) (Perylene-3-yl) butyrate) phenyl) methyl]-4, 5-dihydro-1H-benzo [ g]indolo-N]Boron difluoride): RLE-3 was synthesized in a similar manner to RLE-2 using compound 3.2(0.100mmol, 67mg) and 4- (peren-3-yl) butanoic acid (0.150mmol, 51mg) overnight at room temperature. The compound was purified by flash chromatography on silica gel (100% DCM (1CV) → 10% EtOAc/DCM (10 CV)). The fractions were collected and evaporated to dryness to give 95mg, 95% yield. Ms (apci): c ₅₇ H ₄₁ BBr ₂ F ₂ N ₂ O ₂ (M ^- ) 992; measured value: 992. ¹ h NMR (400MHz, chloroform-d) δ 9.01(d, J ═ 1.3Hz, 1H), 8.27-8.15 (m, 4H), 7.97(d, J ═ 8.4Hz, 1H), 7.68(dd, J ═ 8.1, 4.7Hz, 2H), 7.56(t, J ═ 8.0Hz, 1H), 7.48(td, J ═ 7.8, 1.7Hz, 2H), 7.46-7.39 (m, 3H), 7.12(d, J ═ 8.1Hz, 2H), 6.87(s, 2H), 6.33(s, 2H), 3.21(t, J ═ 7.6Hz, 2H), 2.85(t, J ═ 7.1, 3H), 2.74(t, J ═ 1, 2H), 7.65 (t, J ═ 2H), 7.19(t, 2H), 7.19, 2H).

Example 2.4 RLE-4:

compound 4.1 (3-methyl-4, 5-dihydro-1H-benzo [ g ] indole-2-carboxylic acid tert-butyl ester):

step-1: to a solution of tert-butyl 3-oxobutyrate (10mL) in 20mL HOAc was slowly added NaNO with ice bath cooling ₂ (4.5g) while maintaining the temperature of the reaction mixture between 5-10 ℃. After addition, the whole was stirred at room temperature for one hour, then another 20mL HOAc was added and the resulting oxime solution was used in step 2 without further purification.

Step-2: 1-Tetrahydronaphthalenone (8.8g) with 10g NaOAc were dissolved in 100mL HOAc and the mixture was heated at 100 ℃. To the mixture was added dropwise the oxime solution from step-1 while slowly adding zinc powder. After addition of both oxime and zinc, the whole was heated at 110 ℃ for one hour, then cooled to 70 ℃ and poured into ice water (1.8L). Allowing the mixture to standThe solid was then collected by filtration and purified by flash chromatography (silica gel) (0% → 40%) using an eluent of dichloromethane/hexane. The 4 th fraction was collected and the solvent was removed to give the desired product as a white solid (0.15g, 1% yield). LCMS (APCI +): c ₁₈ H ₂₂ NO ₂ Calculated value of (M + H): 284; measured value: 284.

compound 4.2: to a solution of compound 4.1(150mg, 0.53mmol) in dichloroethane (5mL) was added 1mL 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 (30mg), and the solution was stirred overnight to form dipyrromethane. After removing the solvent under reduced pressure, 6mL of dichloroethane was added to dissolve the resulting product. Tetrachlorop-benzoquinone (65mg) was added to the solution with cooling in an ice water bath and stirred for one hour. Then, BF was added ₃ Ether (0.5mL) and trimethylamine (0.5mL), and the mixture was stirred at room temperature overnight, then treated with 1N HCl (50mL) and extracted with dichloromethane. Collecting the organic phase with MgSO ₄ Dried, loaded on silica gel and purified by flash chromatography using an eluent of dichloromethane/hexane (0% → 80%). The desired red luminescent fraction was collected, and the solvent was removed to give the desired product as a solid (6mg, 5% yield). LCMS (APCI +): c ₃₃ H ₂₈ BF ₂ N ₂ Calculated O (M + H): 517; found value 517.

RLE-4: to a mixture of compound 4.2(6mg, 0.012mmol), 4- (peren-3-yl) butanoic acid (6mg, 0.015mmol), DMAP/p-TsOH salt (6mg, 0.02mmol) in dichloromethane (3mL) was added a solution of DIC (10mg) in 1mL dichloromethane. The mixture was stirred at room temperature overnight, then loaded on silica gel and purified by flash chromatography using an eluent of dichloromethane/hexane (0% → 50%). The desired red luminescent fractions were collected and after removal of the solvent, the desired product was obtained as a dark green solid (3mg, 33% yield). LCMS (APCI +): c ₅₇ H ₄₄ BF ₂ N ₂ O ₂ Calculated value of (M + H): 836; measured value: 836. ¹ h NMR (400MHz, dichloromethane-d) ₂ )δ8.73(d，J＝8.0Hz，2H)，8.30–8.16(m，4H)，8.00(dd，J＝8.4、1.0Hz，2H)，7.70(dd，J＝8.1、4.9Hz，2H)，7.62–7.37(m，8H)，7.37–7.24(m，6H)，3.25–3.17(m，2H)，2.89(t、J＝7.0Hz，4H)，2.76(t、J＝7.2Hz，2H)，2.55(t、J＝7.1Hz，4H)，2.32–2.20(m，2H)，1.40(s，6H)。

Example 2.5 RLE-5

Compound 5.1(1- (2-bromophenyl) cyclopent-1-ol): an oven dried 250mL 2-neck round bottom flask was equipped with a gas connector and stir bar and flushed with argon. The flask was sealed with a septum and charged with magnesium turnings (145mmol, 3.525g) and anhydrous THF (100mL) using a syringe. An oven dried 100mL 2-neck round bottom flask was fitted with a gas connector and flushed with argon. The flask was sealed with a septum and charged with anhydrous THF (60 mL). To a 100mL flask was added 1, 5-dibromopentane (70.0mmol, 8.30 mL). A 250mL flask was cooled in an ice water bath at 0 ℃ and a solution of 1, 5-dibromopentane was added via 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. The reaction became slightly cloudy with stirring at room temperature for 4 hours. A1000 mL 2-neck round bottom flask was equipped with a gas connector and stir bar and flushed with argon. The second neck was sealed with a septum and anhydrous THF (60mL) was added. To the flask was added ethyl 2-bromobenzoate (50.0mmol, 7.94mL) with stirring at room temperature. The flask was cooled to 0 ℃ in an ice-water bath and a solution of the dual format reagent was added via cannula with vigorous stirring for 5 minutes. The reaction mixture was stirred at 0 ℃ for 15 minutes and then at room temperature for 3 hours. The reaction mixture was cooled to 0 ℃ and quenched with saturated ammonium chloride solution (50 mL). The reaction mixture was further diluted with water (500mL) and extracted with ethyl acetate (3 × 150 mL). The combined organic layers were washed with brine (150mL) and MgSO ₄ Dried, filtered and concentrated to a pale yellow oil by rotary evaporation. The oil was used for the next stepThe process is sufficiently pure. 11.145g (92% yield) were obtained. Ms (apci): c ₁₁ H ₁₃ The calculated value of BrO (M + H) is 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): a250 mL 2-neck round bottom flask was equipped with a stir bar and fitted with a gas connector. The flask was flushed with argon and 1- (2-bromophenyl) cyclopent-1-ol (10.0mmol, 2.412g) was added to the flask. Anhydrous dichloromethane (100mL) was added with stirring at room temperature and 1-tosyl-1H-pyrrole (11.0mmol, 2.434g) was added. To the stirred mixture was added aluminum chloride (11.5mmol, 1.533g) in one portion. The reaction was stirred at room temperature under argon overnight. The reaction was quenched with water (30mL) under vigorous stirring. The layers were separated and the aqueous layer was extracted with dichloromethane (3X 25 mL). The combined organic layers were washed with brine (25mL), MgSO ₄ Dried, filtered and evaporated to dryness. The crude product was purified by flash chromatography on silica gel (100% hexane (1CV) → 15% EtOAc/hexane (10 CV)). Both possible isomers eluted as a single peak on silica gel and were also co-eluted with unreacted 1-tosyl-1H-pyrrole, 1.311 g. By passing ¹ H NMR estimated 1.05g of product, 23% yield. The mixture was used in the next step without further purification. Ms (apci): c ₂₂ H ₂₂ BrNO ₂ Calculated value of S (M + H) is 444; measured value: 444.

compound 5.3(2- (1- (2-bromophenyl) cyclopentyl) -1-tosyl-1H-pyrrole): a40 mL screw-capped vial was equipped with a stir bar. To the vial was added a mixture from compound 2.2 (estimated 2.37mmol, 1.05 g). The vial was flushed with argon. To the vial were added potassium carbonate (4.86mmol, 672mg), Pd (PPh) ₃ ) ₄ (0.0711mmol, 82mg), and anhydrous dimethylformamide (6 mL). The vial was purged of oxygen by vacuum/backfill argon cycle (3 ×). The reaction mixture was stirred under argon in a heating block at 110 ℃ overnight. The next morning, more potassium carbonate (4.86mmol, 672mg) and Pd (PPh) were added ₃ ) ₄ (0.0711mmol, 82mg) and at 110 deg.CHeating was continued for another 24 hours. The reaction mixture was cooled to room temperature, diluted with water (100mL), and extracted with ether (3 × 50 mL). The combined organic layers were washed with water (3X 25mL), brine (25mL), and MgSO ₄ Dried, filtered and evaporated to dryness. Purification was by flash chromatography on silica gel (10% DCM/hexane (1CV) → 50% DCM/hexane (10 CV)). Co-eluting the desired product with 1-tosyl-1H-pyrrole, by ¹ The yield estimated by H NMR was 549mg, 64%. The mixture of the desired isomer and 1-tosyl-1H-pyrrole was sent to the next step without further purification. Ms (apci): c ₂₂ H ₂₁ NO ₂ Calculated value of S (M + H) ═ 364; measured value: 364.

compound 5.4(1 'H-Spirocyclo [ cyclopentane-1, 4' -indeno [1,2-b ]]Azole compounds]): a 100mL 2-neck round bottom flask was fitted with a stir bar and equipped with a finned condenser and gas connectors. The flask was flushed with argon and a mixture from compound 2.3 (estimated to be 1.8mmol, 819mg mixture) was added followed by tetrahydrofuran (BHT inhibited, 50mL) and methanol (15 mL). To the flask was added KOH (18.0mmol, 1.01 g). The second neck was stoppered and the flask was placed in a heating block. The reaction mixture was stirred under argon at 65 ℃ for 12 hours. The solvent was evaporated and the residue was dispersed in saturated ammonium chloride (25mL) and water (100 mL). The product was filtered off, dried and purified by flash chromatography on silica gel (100% hexane (1CV) → 20% EtOAc/hexane (10 CV)). The product containing fractions were dried by rotary evaporation to yield 279mg (74% yield) free of any contaminants. Ms (apci): c ₁₅ H ₁₅ The calculated value of N (M + H) is 210; measured value: 210. ¹ h NMR (400MHz, chloroform-d) δ 8.24(s, 1H), 7.33(dt, J ═ 7.5, 1.0Hz, 1H), 7.24 to 7.17(m, 2H), 7.08(td, J ═ 7.2, 1.7Hz, 1H), 6.81(t, J ═ 2.5Hz, 1H), 6.19(dd, J ═ 2.7, 1.8Hz, 1H), 2.16 to 2.02(m, 6H), 1.89 to 1.74(m, 2H).

Compound 5.5(4- (6',6' -difluoro-6 'H-5' l4,6'l 4-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): a250 mL 2-neck round bottom flask was equipped with a finned condenser, stir bar, and gas connectors. The flask was purged with argon, and compound 2.4(1.31mmol, 275mg) and 4-hydroxy-2, 6-dimethylbenzaldehyde (0.683mmol, 103mg) were added, followed by addition of anhydrous dichloroethane (50 mL). The solution was stirred and sparged with argon for 30 minutes, then trifluoroacetic acid (0.1% v/v, 50 μ L) was added via syringe and argon sparging 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 ℃ with an ice-water bath and tetrachlorop-benzoquinone (0.655mmol, 161mg) was added with stirring. The reaction was stirred at 0 ℃ for 20 minutes at which time the oxidation was complete. Addition of BF to the reaction ₃ .OEt ₂ (14.67mmol, 1.8mL) and triethylamine (8.78mmol, 1.2mL), and the mixture was stirred at 0 ℃ 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 ℃ for 6 hours. The reaction mixture was evaporated to dryness and treated with methanol (10mL) 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 (4CV) → 5% EtOAc/DCM (5CV) → 5% EtOAc/DCM. 314mg were obtained in 85% yield. Ms (apci): c ₃₉ H ₃₅ BF ₂ N ₂ O(M ^- ) The calculated value of (d) is 596; measured value: 596.

RLE-5: (4- (6',6' -difluoro-6 'H-5' l4,6'l 4-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-dimethylphenyl 4- (perylene-3-yl) butanoate): a40 mL screw-capped vial was equipped with a stir bar, compound 2.5(0.100mmol, 60mg), 4- (peren-3-yl) butyric acid (0.150mmol, 51mg), and DMAP: pTsOH 1: salt 1 (0.200mmol, 59 mg). The vial was flushed with argon and anhydrous dichloromethane (20mL) was added. Diisopropylcarbodiimide (0.300mmol, 47 μ L) was added and the reaction was stirred at room temperature under argon overnight. The next morning, anhydrous water was addedTetrahydrofuran (10mL) and sonicated for 30 seconds. An additional portion of 4- (peren-3-yl) butyric acid (0.150mmol, 51mg) was added and stirred under argon at 50 ℃ overnight. The solvent was evaporated and the product was purified by flash chromatography on silica gel (100% hexane (1CV) → 5% EtOAc/hexane (0CV) → 40% EtOAc/hexane (10 CV)). The product fractions were evaporated and subjected to a second purification (100% hexane (1CV) → 10% EtOAc/hexane (0CV) → 30% EtOAc/hexane (10 CV)). The fractions containing the pure product were evaporated, yielding 42mg (52% yield). Ms (apci): c ₆₃ H ₅₁ BF ₂ N ₂ O ₂ (M ^- ) 915; measured value: 915.

example 2.6: RLE-6

Compound 6.1(1,4,5, 6-tetrahydrobenzo [6,7]]Cycloheptane [1,2-b ]]Pyrrole): KOH (1.35g), NH ₂ A mixture of oh.hcl (1.67g) in 10mL DMSO was degassed and stirred at room temperature for 30 minutes. To the mixture was added a solution of 1-benzocycloheptane (3.2g) in 10mL of DMSO. The resulting mixture was stirred at 70 ℃ for 30 minutes. KOH (2.0g) was then added and the mixture was heated to 140 ℃ and a solution of 1, 2-dichloroethane (2.38g) in DMSO (10mL) was added dropwise over an 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. times.3). Na for organic phase ₂ SO ₄ Dried, loaded on silica gel and purified by flash chromatography using an eluent of dichloromethane/hexane (0% → 30%). The 2 nd main fraction was collected as the desired product, and after removal of the solvent, a white solid was obtained (0.22g, 8.5% yield). LCMS (APCI +): c ₁₃ H ₁₄ Calculated value of N (M + H): 184, a first electrode; measured value: 184.

compound 6.2: a mixture of compound 8(0.22g, 1.2mmol), 4-hydroxy-2, 5-dimethylbenzaldehyde (0.09ng, 0.6mmol) and one drop of TFA in dichloroethane was degassed for 30 minutes and then heated at 40 ℃ overnight. After cooling to room temperatureAfter that, it was cooled in an ice-water bath, tetrachlorop-benzoquinone (0.2g) was added, and the mixture was stirred for 20 minutes. Then BF was added ₃ Ether (0.8mL) and trimethylamine (0.5 mL). The mixture was heated at 50 ℃ for two hours, then loaded on silica gel and purified by flash chromatography using an eluent of dichloromethane/hexane (10% → 90%). After removal of the solvent, the desired product was obtained (54mg, 16% yield). LCMS (APCI 1): c ₃₅ H ₃₀ BF ₂ N ₂ Calculated value of O (M-H): 543; measured value: 543.

RLE-6: to a mixture of compound 9(54mg, 0.1mmol), 4- (peren-3-yl) butanoic acid compound 5(50mg, 0.15mmol), DMAP/p-TsOH salt (60mg, 0.2mmol) in 7mL of dichloromethane was added a solution of DIC (60mg, 0.5mmol) in 1mL of dichloromethane. The mixture was stirred at room temperature overnight and then loaded on silica gel and purified by flash chromatography using an eluent of dichloromethane/hexane (10% → 70%). The desired fractions were collected and the solvent was removed to give a solid (75mg, 87% yield). LCMS (APCI-): c ₅₉ H ₄₇ BF ₂ N ₂ O ₂ (M ^- ) The calculated value of (a): 864; measured value: 864. ¹ h NMR (400MHz, dichloromethane-d) ₂ )δ8.35–8.21(m，4H)，8.05(d，J＝8.7Hz，2H)，7.74(dd，J＝8.1、5.0Hz，2H)，7.67–7.59(m，1H)，7.59–7.46(m，3H)，7.38(td，J＝6.0、5.5、3.5Hz，4H)，7.33(q、J＝5.1、4.4Hz，2H)，6.96(s，2H)，6.47(s，2H)，5.37(s，15H)，3.29–3.21(m，2H)，2.79(t、J＝7.2Hz，2H)，2.66(t、J＝6.8Hz，4H)，2.32(d，J＝7.3Hz，3H)，2.29(s，6H)，2.07(p、J＝7.0Hz，4H)。

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 tert-butyl ester): step 1. tert-butyl 3-oxobutyrate (10mL) was dissolved in acetic acid (20mL) and the solution was cooled with an ice bath. To this solution was added sodium nitrite (4.5g) in bulk while the mixture was kept at 10 ℃. After one hour, the ice bath was removed and the mixture was allowed to warm to room temperature and stirred for one hour to form an oxime solution.

Step 2. to the solution prepared above, a solution of 1-benzocycloheptane (3.2g) in 25mL of acetic acid was added, followed by addition of zinc powder (11.25g) in portions. The resulting mixture was stirred at 75 ℃ for one hour, then the mixture was cooled to room temperature, then 10mL of water was added, and left to stand for one hour. The solid was filtered off, and the filtrate was poured into 100mL of water and left overnight. The resulting solid was collected by filtration and redissolved in dichloromethane and loaded on silica gel for purification by flash chromatography using an eluent of dichloromethane/hexane (0% → 90%). The desired product was collected as fraction 2. After removal of the solvent, a white solid was obtained (0.15g, yield 2.5%). LCMS (APCI +): c ₁₉ H ₂₄ NO ₂ Calculated value of (M + H): 298; measured value: 298.

compound 7.2: compound 7.1(50mg, 0.168mmol) was dissolved in 1.5mL of TFA. The solution was degassed for 10 minutes while stirring. LCMS indicated decarboxylation of all compound 7.1 to the desired pyrrole. To this mixture was added 3mL of dichloroethane, followed by 10mg of 4-hydroxybenzaldehyde. The mixture was degassed for 10 minutes and stirred overnight. LCMS indicated the main product as dipyrromethane product. To the mixture was added tetrachlorop-benzoquinone (20mg, 0.084mmol) at 0 ℃ and stirred for 10 min. Then 0.4mL of BF was added ₃ Ether and 1mL of trimethylamine, the resulting mixture was stirred at room temperature overnight and then loaded on silica gel and purified by flash chromatography using an eluent of dichloromethane/hexane (0% → 80%). After removal of the solvent, the desired product was obtained (5mg, 12% yield). LCMS (APCI-): c ₃₅ H ₃₀ BF ₂ N ₂ Calculated value of O (M-H): 543; measured value: 543.

RLE-7: a mixture of compound 7.2(5mg, 0.01mmol), 4- (peren-3-yl) butyric acid (5mg, 0.015mmol), DMAP/p-TsOH salt (6mg, 0.02mmol), and DIC (10mg) in 2mL of dichloromethane was stirred at room temperature overnight,then loaded on silica gel and purified by flash chromatography using an eluent of dichloromethane/hexane (0% → 35%), collecting orange red fractions, and removing the solvent gave a solid (3mg, 35% yield). LCMS (APCI-): c ₅₉ H ₄₇ BF ₂ N ₂ O ₂ Calculated value of (M-): 864; measured value: 864.

example 2.8 RLE-8

4- (Perylenel-3-yl) butanoic acid methyl ester

Step 1: in a 1L two-necked flask equipped with a magnetic stir bar, powder distributor funnel, the yellow suspension mixture of perylene (5.22g, 20.68mmol) in anhydrous DCM (500mL) was stirred on a chilled ice + water bath and bubbled with argon for 15 min; methyl 4- (4,12 b-dihydroperylene-3-yl) butyrate (3.425g, 22.75mmol) was added slowly via syringe and needle. The cooling bath was removed and the mixture was allowed to stir at room temperature for 15 minutes. The mixture was cooled again with ice + water bath; AlCl addition in small portions via powder distributor funnel ₃ (3.3g, 24.74 mmol). The resulting dark purple mixture was stirred at room temperature under argon for 16 hours. TLC and LCMS showed almost complete consumption of starting material. The reaction mixture was diluted with 500mL of DCM, then ice + water (150mL of water) was poured in, the organic layer was separated and MgSO ₄ Drying and concentrating to 100 mL; mixing SiO ₂ (100g) Added to THE tee solution mixture to absorb THE product, then loaded on a column (330g) eluting with 1 hexane/DCM (100: 0) → (0: 100) to afford 1.25g of THE desired product. The product from column chromatography and the solid product from filtration were combined and purified by hexane: EtAco (9: 1) recrystallised gave 4.24g of a yellow solid in 56% yield. LCMS (APCI +), formula: c ₂₅ H ₁₈ O ₃ The calculated value of (a); measured value: 366. ¹ h NMR (400MHz, chloroform-d) δ 8.57(dd, J ═ 8.6, 1.0Hz, 1H), 8.30-8.17 (m, 4H), 7.97(d, J ═ 8.1Hz, 1H), 7.78(d, J ═ 8.1Hz, 1H), 7.73(d, J ═ 8.1Hz, 1H), 7.64-7.48 (m, 3H), 3.75(s, 3H), 3.41(t, J ═ 6.5Hz, 2H), 2.86(t, J ═ 6.5Hz, 2H).

Step 2: a yellow mixture of the product of the above step (4.24g, 11.58mmol) in anhydrous DCM (100mL) was stirred over a cooled ice + water bath in 250mL RB and bubbled with argon for 15 min; TFA (25mL) was added slowly. The cooling bath was removed to allow the mixture to stir at room temperature for 15 minutes; triethylsilane (15mL) was added immediately. The resulting dark mixture was stirred at room temperature under argon for 16 hours. TLC and LCMS showed consumption of starting material. The reaction mixture was diluted with 200mL of DCM and then placed on a rotary evaporator. TFA and DCM were concentrated. The residue was redissolved in DCM (50mL) and the mixture was concentrated to dryness. The dark crude product was loaded on SiO ₂ On the column, eluting with 1 hexane/EtAcO (95: 5), 4.00g of the product was obtained as a yellow solid. The yield was 98%. LCMS (APCI +), formula: c ₂₅ H ₂₀ O ₂ The calculated value of (a); measured value: 352.

4- (4, 9-dibromo-4, 12 b-dihydroperylene-3-yl) butyric acid methyl ester/4- (4, 10-dibromo-4, 12 b-dihydroperylene-3-yl) butyric acid methyl ester

A mixture of the compound methyl 4- (4,12 b-dihydroperylene-3-yl) butyrate (1.00g, 4.36mmol) and NBS (1.9g, 10.9mmol) in anhydrous DCM (45mL) was stirred at room temperature and purged with argon for 15 minutes before anhydrous DMF (5mL) was added. The resulting mixture was stirred at room temperature for 3 hours; TLC and LCMS showed consumption of starting material. 20mL of water and 50mL of DCM were added, and the organic layer was washed several times with water and MgSO ₄ Drying and concentrating. Passing the crude product through SiO ₂ Purification by column chromatography, eluting with 1 hexane/EtAcO (95: 5), gave 1.25g of a mixture of the two isomers of the dibromoperylene derivative in 56% yield.

LCMS (APCI +), formula: c ₂₅ H ₁₈ Br ₂ O ₂ The calculated value of (a); measured value: 510.

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

A mixture of the compound methyl 4- (4,12 b-dihydroperylene-3-yl) butyrate (1.00g, 2.837mmol, 1 equivalent) in anhydrous DCM (20mL) was placed in a two-necked flask and kept in the dark. The mixture was purged with argon for 15 minutes and NBS (1.767g, 9.929mmol, 3.5 equivalents) was added in small portions and then stirred at room temperature for 15 minutes. Anhydrous DMF (10mL) was added. The resulting mixture was stirred at room temperature under argon for 4 hours. TLC and LCMS showed consumption of starting material. 25mL of water was added and the organic layer was separated; the aqueous layer was re-extracted with ethyl acetate, washed several times with water, over MgSO ₄ Drying and concentrating. Passing the crude product through SiO ₂ Purification by column chromatography eluting with hexane/DCM (9: 1) to (1: 4) gave 0.655g of tribromoperylene derivative: dibromo perylene derivatives: a mixture of three isomers (7: 1: 0.5) of tetrabromoperylene derivative. The product was carried on to the next step without further purification. The yield was 38%. LCMS (APCI +), formula: c ₂₅ H ₁₇ Br ₃ O ₂ The calculated value of (a); measured value: 589.

one isomer is drawn for illustration. The actual reaction is a mixture of brominated isomers of the starting material and trifluoromethylated isomers of the product.

A100 mL 2-neck round bottom flask was set up. A stir bar, finned condenser, and gas connector were added. The flask and condenser were flushed with argon. Stirring under argon, adding CuI (10.0 equiv., 13.6mmol,2.586g) was added to the flask. The brominated perylene isomer (1.0 equivalent, 1.36mmol, 800mg) was dissolved in 5mL of anhydrous DMA under an argon atmosphere and transferred to a flask via syringe. The vial was rinsed with dry DMA (2 x 5mL) under an argon atmosphere and aliquots of these DMAs were also added to the reaction flask. An additional 15mL of anhydrous DMA was added to the reaction flask (total DMA ═ 30 mL). Methyl 2- (fluorosulfonyl) -2, 2-difluoroacetate (10.0 eq, 13.6mmol, 2.609g, 1.509g/mL, 1.73mL) was added to the flask by syringe and the second neck was sealed with a glass stopper. The mixture was stirred and heated with a heating block set to 160 ℃. After 2 hours LCMS indicated reaction completion of about 90%. CuI (5.0 equiv., 6.80mmol, 1295mg) and methyl 2- (fluorosulfonyl) -2, 2-difluoroacetate (5.0 equiv., 6.80mmol, 1306mg, 1.509g/mL, 0.866mL) were added and the reaction was stirred at 160 ℃ for 2h then at room temperature overnight. The reaction mixture is worked up by; the reaction mixture was poured into 700mL of stirred water and the reaction flask was washed with water and a little methanol. The volume was adjusted to 900mL with water and the suspension was filtered through a thin layer of celite (slow filtration) and the filter cake was washed with water. The wet cake and filter paper were broken up and first stirred in acetone (20mL) and then DCM (500mL) was added with stirring. The organic layer was filtered through a second pad of celite, transferred to a separatory funnel and separated from the water, using MgSO ₄ Dried, filtered and concentrated to dryness. The mixture was purified by flash chromatography (first wavelength 300nm, 2 nd wavelength 440nm), 220g column, equilibrated with 50% toluene/hexane, dissolved and loaded in 2: 1, hexane: in toluene, the elution was carried out with 50% (1CV) → 100% toluene (10 CV). The desired fraction shows a strong UV peak at 440 nm.

Fractions were grouped into early eluting mixtures, middle peaks, and late eluting fractions. Early eluting fractions were traces of mixed Br/CF ₃ Isomers were discarded. The middle peak is mainly tri-CF ₃ Isomer, 204mg (yield 26.9%). Late eluting fraction ═ di-CF ₃ tri-CF ₃ And tetra-CF ₃ Mixed isomer, 75mg (10% yield).

Separating the two isomers into pure compounds; NMR and LCMS determined two structures as shown below:

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

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

(4,9, 10-tris (trifluoromethyl) perylene-3-yl) butanoic acid

A mixture of methyl 4- (4,9, 10-tris (trifluoromethyl) perylen-3-yl) butyrate (40mg, 0.0718mmol), 5M aqueous KOH (0.143mL, 0.718mmol), THF (2mL), MeOH (0.5mL) was stirred at 65 ℃ for 6 h. After cooling to 0 ℃, the mixture was acidified with 6N aqueous HCl to pH 4-5 and then poured into water; extract with DCM and MgSO ₄ Drying, concentration to dryness gave 38mg of product as a red solid in 98% yield. The product was used in the next step without further purification. LCMS (APCI +), formula: c ₂₇ H ₁₅ F ₉ O ₂ Calculated value of (a), found value: 542.40

RLE-8: ((T-4) - [2- [ (4, 5-dihydro-8-bromo-2H-benzo [ g)]Indol-2-ylidene-kN) - (3, 5-dimethyl-4- (- ((4- (4,9, 10-tris (trifluoromethyl) perylene-3-yl) butyryl) oxy) phenyl) methyl]-4, 5-dihydro-1H-benzo [ g]indolo-kN]Difluoro boron): which consists of the compound 6.2 (described above) [2- [ (4, 5-dihydro-8-bromo-2H-benzo [ g ]]indol-2-ylidene-kN) - (3, 5-dimethyl-4-hydroxyphenyl) methyl]-4, 5-dihydro-1H-benzo [ g]indolo-kN]Difluoro boron (0.100mmol, 52mg) and ((4,9, 10-trifluoromethyl) perylene-3-yl) butyric acid) (0.100mmol, 55mg) were synthesized. The crude product was purified by flash chromatography on silica gel (80% toluene/hexane (1CV) → 100% toluene (5 CV)). The fractions containing the product were evaporated to dryness to yield 77mg (74% yield). Ms (apci): the chemical formula is as follows: c ₆₀ H ₄₀ BF ₁₁ N ₂ O ₂ (M-) 1040; measured value: 1040.

example 2.9 RLE-9

Compound 9.1 (3-methyl-4, 5-dihydro-1H-benzo [ g)]Indole-2-carboxylic acid ethyl ester): a250 mL 2-neck round bottom flask was equipped with a stir bar and placed in a heating block. To the flask were added 1-tetralone (100.0mmol, 14.620g) and sodium propionate (100.0mmol, 9.610g), followed by acetic acid (50 mL). The reaction was heated to 145 ℃ with stirring while leaving air open. Ethyl 2- (hydroxyimino) -3-oxobutanoate (2.50mmol, 398mg) and Zn (powder,<10 μm) (12.5mmol, 818mg) were charged into a 40mL screw cap vial. These materials were slurried in acetic acid (12.5mL) and added portionwise over a period of about 5 minutes to a stirred reaction containing the ketone. This process was repeated 3 times for a total of 10.0mmol of 2- (hydroxyimino) -3-oxobutanoate and 50.0mmol of Zn powder. The reaction was stirred at 145 ℃ for 2.5 hours and then cooled to room temperature. The reaction was quenched by pouring water (600mL) with stirring. The volume was brought to 900mL with water and then extracted with dichloromethane (4X 160 mL). The combined organic layers were washed with water (100mL), brine (100mL), MgSO ₄ Dried, filtered and evaporated to dryness. Most of the excess 1-tetralone is removed under high vacuum with heating.The crude product was purified by flash chromatography on silica gel (5% EtOAc/hexanes (1CV) → 20% EtOAc/hexanes (10 CV)). The fractions containing the product were evaporated to dryness to yield 1.417g (55% yield). Ms (apci): the chemical formula is as follows: c ₁₆ H ₁₇ NO ₂ The calculated value of (M + H) is 256; measured value: 256. ¹ H NMR(400MHz)δ8.98(s，1H)，7.35–7.31(m，1H)，7.27–7.21(m，2H)，7.20–7.15(m，1H)，4.34(q，J＝7.1Hz，2H)，2.99–2.92(m，2H)，2.70–2.64(m，2H)，2.31(s，3H)，1.39(t，J＝7.1Hz，3H)。

compound 9.2 (3-methyl-4, 5-dihydro-1H-benzo [ g)]Indole): a 250mL 2-neck round bottom flask was fitted with a stir bar and equipped with a finned condenser and gas connectors. The flask was flushed with argon and compound 9.1(5.01mmol, 1.278g) was added to the flask followed by ethylene glycol (50 mL). To the reaction mixture was added KOH (in H) ₂ 5.0M in O, 25.03mmol, 5.01 mL). The reaction was stoppered and heated in a heating block at 100 ℃ for 90 minutes under argon. The solution was made homogeneous under heating. The temperature was raised to 160 ℃ for 30 minutes and then cooled to 100 ℃. The reaction was quenched by pouring stirred water (300 mL). The total volume was made 500mL with water and then acidified with a solution of 2.5M acetic acid/2.5M NaOAc (20 mL). The pH was lowered to 3.5 with TFA. The resulting purple solid was filtered off, dried, and purified by flash chromatography on silica gel (5% EtOAc/hexanes (1CV) → 20% EtOAc/hexanes (10 CV)). The product containing fractions were evaporated to dryness to give 767mg (84% yield). Ms (apci): the chemical formula is as follows: c ₁₃ H ₁₃ The calculated value of N (M + H) was 184, found: 184. ¹ h NMR (400MHz, acetonitrile-d) ₃ )δ9.15(s，1H)，7.24(d，J＝7.5Hz，1H)，7.20–7.13(m，2H)，7.00(td，J＝7.4，1.4Hz，1H)，6.52(dd，J＝2.3，0.9Hz，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-. kappa.N) (3, 5-dimethyl-4-hydroxyphenyl) methyl]-4, 5-dihydro-3-methyl-1H-benzo [ g]Indolo-kappa N]Difluoro boron): compound 9.3 is prepared in a similar manner to compound 3.2 fromCompound 9.2(3.97mmol, 728mg) and 4-hydroxy-2, 6-dimethylbenzaldehyde (2.02mmol, 304mg) were synthesized. The crude product was purified by flash chromatography on silica gel (100% toluene (2CV) → 10% EtOAc/toluene (10 CV)). The fractions containing the product were evaporated to yield 563mg (3 steps from pyrrole, 52% yield). Ms (apci): the chemical formula is as follows: c ₃₅ H ₃₁ BF ₂ N ₂ Calculated O (M + H) is 544, found: 544. ¹ H NMR(400MHz，DMSO-d ₆ )δ9.61(s，1H)，8.62(d，J＝7.9Hz，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) butyryl) oxy) phenyl) methyl]-4, 5-dihydro-3-methyl-1H-benzo [ g]Indolo-kappa N]Difluoro boron): RLE-9 was synthesized in a similar manner as compound 2 (described above) from compound 9.3(0.116mmol, 63mg) and (4,9, 10-tris (trifluoromethyl) perylen-3-yl) butanoic acid (0.116mmol, 63 mg). The crude product was purified by flash chromatography on silica gel (60% toluene/hexane (2CV) → 100% toluene (isocratic)). The fractions containing the product (as a mixture of isomers) were evaporated to dryness to yield 84mg (68% yield). Ms (apci): the chemical formula is as follows: c ₆₂ H ₄₄ BF ₁₁ N ₂ O ₂ (M ^- ) Calculated value of 1068, found: 1068

Example 2.10 RLE-10

Compound 10.1: to 3-methyl-4, 5-dihydro-1H-benzo [ g ] at room temperature under an argon atmosphere]A solution of indole (3.55mmol, 652mg) and 4-hydroxybenzaldehyde (1.77mmol, 216mg) in dry 1, 2-dichloroethane (35.0mL) was added TFA (35.0. mu.L). The reaction mixture was stirred at room temperature for 70 minutes, cooled to 0 ℃ and tetrachlorop-benzoquinone (1.77mmol, 435mg) was added in one portion and stirring was continued for 15 minutes. Adding threeEthylamine (10.6mmol, 1.48mL) and the mixture was warmed to room temperature over 10 minutes, followed by addition of BF ₃ ·OEt ₂ (15.9mmol, 1.96mL) and stirring was continued for 75 minutes. More triethylamine (10.6mmol, 1.48mL) and BF were added ₃ ·OEt ₂ (15.9mmol, 1.96mL), the mixture was stirred for a further 75 minutes and all volatiles were removed under reduced pressure. The residue was diluted with EtOAc (100mL), washed with 1M HCl (2X 100mL) and 6M HCl (100mL), and dried (MgSO) ₄ ) And concentrated under reduced pressure. Flash Chromatography (CH) ₂ Cl ₂ ) 130mg of 10.1 (yield 17%) are obtained as a dark blue/green powder.

¹ H NMR(400MHz，TCE-d ₂ )δ8.74(d，J＝8.0Hz，2H)，7.43(ddd，J＝8.5,8.0,1.7Hz，2H)，7.39–7.24(m，6H)，7.02(d，J＝8.5Hz，2H)，5.05(s，1H)，2.89(dd，J＝8.3,5.9Hz，4H)，2.56(dd，J＝8.3，5.9Hz，4H)，1.44(s，6H)。

RLE-10: (T-4) - [2- [ (4, 5-dihydro-8-bromo-2H-benzo [ g ]]Indol-2-ylidene-kappa N) - (4' - (4- (tris (trifluoromethyl) perylene-3-yl) butoxy) phenyl) methyl]-4, 5-dihydro-1H-benzo [ g]Indolo-kappa N]Boron difluoride: to a solution of 10.1(0.080mmol, 41mg), 4- (tris (trifluoromethyl) perylen-3-yl) butyric acid (0.084mmol, 46mg) and DMAP pTsOH salt (0.160mmol, 47mg) in anhydrous 1, 2-dichloroethane (10.0mL) was added DIC (0.480mmol, 75.0 μ L) under an argon atmosphere at room temperature, and the reaction mixture was stirred at room temperature for 2 hours, then at 50 ℃ for 1 hour. The mixture was then cooled to room temperature, more 4- (tris (trifluoromethyl) perylen-3-yl) butanoic acid (0.055mmol, 30mg) was added and stirring was continued for 16 h. The mixture was diluted with hexane (6.00mL) and purified by flash chromatography (9: 1 hexane/CH) ₂ Cl ₂ → 3: 7 Hexane/CH ₂ Cl ₂ ) To purify, 73.7mg of RLE-10 (89% yield) was obtained as a dark purple powder.

¹ H NMR(400MHz，TCE-d ₂ )δ8.76(d，J＝8.1Hz，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＝7.6Hz，6H)。

EXAMPLE 2.11 Compound RLE-11

Compound 11.1 (4-formyl-3, 5-dimethylphenyl 4- (perylene-3-yl) butyrate): compound 11.1 was synthesized from 4-hydroxy-2, 6-dimethylbenzaldehyde (1.89mmol, 284mg) and 4- (perylene-3-yl) butyric acid (0.946mmol, 320mg) in a similar manner to RLE-2. The crude product was purified by flash chromatography on silica gel (100% toluene, (5CV) → 10% EtOAc/toluene (10 CV)). The fractions containing the product were evaporated to dryness. 296mg (yield 66.5%) of an orange solid are obtained. Ms (apci): the chemical formula is as follows: c ₃₃ H ₂₆ O ₃ Calculated value of (M-) is 470, found: 470. ¹ H NMR(400MHz，TCE-d ₂ )δ10.52(s，1H)，8.25(d，J＝7.5Hz，1H)，8.23–8.17(m，2H)，8.16(d，J＝7.8Hz，1H)，7.94(d，J＝8.4Hz，1H)，7.72(d，J＝5.1Hz，1H)，7.70(d，J＝5.1Hz，1H)，7.57(t，J＝8.0Hz，1H)，7.51(t，J＝7.8Hz，1H)，7.51(t，J＝7.8Hz，1H)，7.40(d，J＝7.7Hz，1H)，6.84(s，2H)，3.17(t，J＝7.6Hz，2H)，2.72(t，J＝7.2Hz，2H)，2.58(s，6H)，2.23(p，J＝7.3Hz，2H)。

the compound RLE-11((T-4) - [2- [ (4, 5-dihydro-8-fluoro-2H-benzo [ g ]]Indol-2-ylidene- κ N) (3, 5-dimethyl-4- (4- (perylene-3-yl) butyrate) phenyl) methyl]-4, 5-dihydro-8-fluoro-1H-benzo [ g]Indolo-kappa N]Difluoro-boron): compound RLE-11 is composed of compound 21.2 (200. mu. mol), compound 11.1 (105. mu. mol, 49.4mg), tetrachlorop-benzoquinone (100. mu. mol, 24.5mg), triethylamine (600. mu. mol, 84. mu.L), and BF in a similar manner to compound 21 ₃ .OEt ₂ To synthesize. The crude product was purified by flash chromatography on silica gel (100% isocratic toluene). The fractions containing the product were evaporated to dryness. 74mg (82% yield based on Compound 21.2) were obtained. Ms (apci): the chemical formula is as follows: c ₅₈ H ₄₅ BF ₄ N ₂ O ₂ Calculated value of (M-)888, found: 888.

example 2.12 RLE-12

3-methyl-1, 4-dihydroindeno [1,2-b ] pyrrole-2-carboxylic acid ethyl ester (12.1)

To a mixture of 1-indanone (30.0mmol, 3.96g), Zn particles-20 mesh (50.0mmol, 3.27g), and sodium propionate (5.00mmol, 480mg) in pentanoic acid (20.0mL) at 180 deg.C was added a solution of ethyl 2- (hydroxyimino) -3-oxobutanoate (10.0mmol, 1.59g) in pentanoic acid (10.0mL) by syringe pump for 1 hour. After complete addition, the reaction mixture was stirred for an additional 15 minutes, then cooled to room temperature and partitioned between 6M HCl (100mL) and EtOAc (100 mL). The aqueous layer was extracted with EtOAc (3X 100mL), and the combined organic layers were washed with 1m aqueous NaOH (3X 200mL) and dried (MgSO) ₄ ) And concentrated under reduced pressure. Reprecipitation from EtOH gave 505mg of compound 12.1 (21% yield) as a colorless solid.

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

3-methyl-1, 4-dihydroindeno [1,2-b ] pyrrole (Compound 12.2)

To a suspension of compound 12.1(0.161mmol, 388mg) and sodium hydroxide (4.82mmol, 193mg) in ethylene glycol (16mL) was added water (500 μ L) and the reaction mixture was stirred at 150 ℃ for 1 hour. It was then cooled to room temperature and 1.0M NH was added ₄ Aqueous Cl (50.0 mL). The precipitate was isolated by vacuum filtration and air dried to give 264mg of compound 12.2 (97% yield) as a purple solid.

¹ H NMR (400MHz, acetonitrile-d) ₃ )δ9.17(br s，1H)，7.42(d，J＝7.4Hz，1H)，7.35(d，J＝7.5Hz，1H)，7.22(dd，J＝7.4，7.5Hz，1H)，7.03(ddd，J＝7.5，7.5，1.2Hz，1H)，6.61(dd，J＝2.3，1.1Hz，1H)，3.38(s，2H)，2.11(s，3H)。

4- (6, 6-difluoro-13, 15-dimethyl-12, 16-dihydro-6H-5 l4,6l 4-indeno [2', 1': 4,5] pyrrolo [1,2-c ] indeno [2', 1': 4,5] pyrrolo [2,1-f ] [1,3,2] diazaborin-14-yl) -3, 5-dimethylphenyl 4- (perylenel-3-yl) butanoate (RLE-12)

To compound 12.2(0.467mmol, 79.0mg) and pTsOH. H at room temperature under an argon atmosphere ₂ To a solution of O (0.005mmol, 1.00mg) in anhydrous 1, 2-dichloroethane (5.00mL) was added compound 12.3(0.212mmol, 100 mg). The reaction mixture was stirred at room temperature for 3 hours, then cooled to 0 ℃, tetrachlorop-benzoquinone (0.212mmol, 52.0mg) was added in one portion and stirring was continued for 15 minutes. Triethylamine (1.27mmol, 177. mu.L) was added and the mixture was warmed to room temperature over 10 minutes, followed by addition of BF ₃ ·OEt ₂ (1.91mmol, 235. mu.L) and stirring was continued for another 30 minutes. The reaction mixture was diluted with EtOAc (30.0mL), washed with 1M HCl (3X 30.0mL) and saturated aqueous NaCl (30.0mL), and dried (MgSO) ₄ ) And concentrated under reduced pressure. Flash chromatography (toluene) gave 96.0mg of RLE-12 (54% yield) as a dark purple powder.

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

Example 2.13 RLE-13

Under argon atmosphere at room temperature to 12.2(0.086mmol, 15.0mg) and pTsOH. H ₂ O (1 crystal) in anhydrous CH ₂ Cl ₂ To the solution (0.90mL) was added 13.1(0.039mmol, 26.0 mg). Will reactThe mixture was stirred at room temperature for 1 hour, then it was cooled to 0 ℃, tetrachlorop-benzoquinone (0.039mmol, 10.0mg) was added in one portion and stirring was continued for 15 minutes. Triethylamine (0.234mmol, 33.0. mu.L) was added and the mixture was warmed to room temperature over 10 minutes, followed by addition of BF ₃ ·OEt ₂ (0.351mmol, 43.0. mu.L) and stirring was continued for another 30 minutes. The reaction mixture was diluted with EtOAc (5.00mL), washed with 1M HCl (3X 5.00mL) and saturated aqueous NaCl (5.00mL), and dried (MgSO) ₄ ) And concentrated under reduced pressure. Flash chromatography (toluene) afforded 16.0mg of RLE-13 (38% yield) as a dark purple/green powder.

¹ H NMR (400MHz, chloroform-d) δ 8.40(d, J ═ 7.9Hz, 2H), 8.34-7.62 (m, 8H), 7.53-7.42 (m, 4H), 7.36 (apparent t, J ═ 7.5Hz, 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-methylcrotonic acid (19.0mmol, 1.90g) in benzene (10.0mL) was slowly added to AlCl in a 100mL round bottom flask ₃ (57.0mmol, 7.60 g). The resulting mixture was heated to reflux for 5h, cooled to 0 ℃, quenched with 1M HCl (50.0mL) and extracted with EtOAc (3 × 50.0 mL). The combined organic layers were washed with saturated NaHCO ₃ The aqueous solution (3X 100mL) and saturated aqueous NaCl solution (100mL) were washed and dried (MgSO ₄ ) And concentrated under reduced pressure. Flash chromatography (9: 1, hexanes/EtOAc) afforded 2.62g of 14.1 (86% yield) as an orange oil.

¹ H NMR (400MHz, 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 (101MHz, chloroform-d) delta 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)

To a mixture of 14.1(3.12mmol, 500mg), Zn particles-20 mesh (15.6mmol, 1.02g) and sodium propionate (1.56mmol, 150mg) in pentanoic acid (12.5mL) at 180 ℃ was added a solution of ethyl 2- (hydroxyimino) -3-oxobutanoate (4.68mmol, 750mg) in pentanoic acid (2.50mL) by a syringe pump for 1 hour. After the addition was complete, the reaction mixture was stirred for an additional 15 minutes, then cooled to room temperature and partitioned between 6M HCl (25.0mL) and EtOAc (25.0 mL). The aqueous layer was extracted with EtOAc (3X 25.0mL) and the combined organics were dried (MgSO) ₄ ) And concentrated under reduced pressure. Flash chromatography (9: 1, hexanes/EtOAc) afforded 42mg of 14.2 (5% yield) as a colorless solid. ¹ H NMR (400MHz, chloroform-d) δ 9.19(s, 1H), 7.40-7.34 (m, 2H), 7.27-7.18 (m, 2H), 4.38(q, J ═ 7.1Hz, 2H), 2.47(s, 3H), 1.51(s, 6H), 1.40(t, J ═ 7.1Hz, 3H).

3,4, 4-trimethyl-1, 4-dihydroindeno [1,2-b ] pyrrole (14.3)

To a suspension of 14.2(0.149mmol, 42mg) and sodium hydroxide (0.446mmol, 18.0mg) in ethylene glycol (1.50mL) was added water (50.0. mu.L) and the reaction mixture was stirred at 150 ℃ for 1 hour. It was then cooled to room temperature and 1.0M NH was added ₄ Aqueous Cl (5.00 mL). CH for the mixture ₂ Cl ₂ Extraction (3X 10.0mL) gave 29mg of 12.2 (99% yield) as a purple solid.

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

4- (6, 6-difluoro-12, 12,13,15,16, 16-hexamethyl-12, 16-dihydro-6H-5. lambda ⁴ ,6λ ⁴ -indeno [2', 1': 4,5]Pyrrolo [1,2-c]Indeno [2', 1': 4,5]Pyrrolo [2, 1-f)][1,3,2]Diazaborane-14-yl) -3, 5-dimethylphenyl 4- (tris (trifluoromethyl) perylene-3-yl) butanoate (RLE-14)

Under argon atmosphere at room temperature to 14.3(0.071mmol, 14.0mg) and pTsOH. H ₂ O (1 crystal) in anhydrous CH ₂ Cl ₂ To the solution (0.70mL) was added 13.1(0.039mmol, 26.0 mg). The reaction mixture was stirred at room temperature for 1 hour, then cooled to 0 ℃, tetrachlorop-benzoquinone (0.036mmol, 9.00mg) was added in one portion and stirring was continued for 15 minutes. Triethylamine (0.216mmol, 30.0. mu.L) was added and the mixture was warmed to room temperature over 10 minutes, followed by addition of BF ₃ ·OEt ₂ (0.324mmol, 40.0. mu.L) and stirring was continued for another 30 minutes. The reaction mixture was diluted with EtOAc (5.00mL), washed with 1M HCl (3X 5.00mL) and saturated aqueous NaCl (5.00mL), and dried (MgSO 5) ₄ ) And concentrated under reduced pressure. Flash chromatography (1: 1 hexane/toluene → toluene) afforded 8.00mg of RLE-14 (21% yield) as a dark purple/green powder.

¹ H NMR (400MHz, 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, 7.0Hz, 2H), 2.36-2.23 (m, 8H), 1.53(s, 6H), 1.50(s, 12H).

Example 2.15 RLE-15 and example 2.16 RLE-16

Compound 15.1 (7-bromo-3-methyl-4, 5-dihydro-1H-benzo [ g)]Indole-2-carboxylic acid ethyl ester): to a 250mL 2-necked round bottom flask was added a stir bar, 6-bromo-3, 4-dihydronaphthalen-1 (2H) -one (20.0mmol, 4.502g), sodium propionate (5.00mmol, 480mg), and Zn (particles, 10-20 mesh, 50.0mmol, 3.270 g). The flask was fitted with a finned condenser and gas connectors. The flask was flushed with argon and propionic acid (20mL) was added. A solution of ethyl acetoacetate-2-oxime (10.0mmol, 1.591g) was prepared in propionic acid (10 mL). The reaction flask was placed in an aluminum heating block and preheated to 160 ℃. The solution of ethyl acetoacetate-2-oxime was added over a period of 60 minutes by a syringe pump. Crude LCMS indicates product and dehydrohalogenated product as well as unreacted starting material and dehydrohalogenatedRaw materials. 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 (1X 200mL, 1X 100mL), 1N aqueous NaOH (2X 50mL), and brine (50 mL). The organic layer was washed with MgSO ₄ Dried, filtered and concentrated to an oil. The oil was diluted with hexane (50mL) and allowed to stand overnight at room temperature. The resulting 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 (2CV) → 10% EtOAc/hexane (20 CV)). The fractions containing the product were evaporated to dryness. The product purified from silica gel was combined with the crystals to give pure product. ¹ H NMR indicates two pyrrole-Me groups at 1: a ratio of 2 exists. LCMS showed the main product to be dehydrohalogenated. 1.077g (yield-38.2%, based on having a structure derived from ¹ Blend MW of ratio of H NMR). Both are not separable on silica gel. Used in the next step without further purification. Ms (apci): the chemical formula is as follows: c ₁₆ H ₁₆ BrNO ₂ The calculated value of (M + H) is 334, found: 334. ms (apci): the chemical formula is as follows: c ₁₆ H ₁₇ NO ₂ The calculated value of (M + H) was 256, found: 256. ¹ H NMR(400MHz，TCE-d ₂ ) δ 9.00(s, 1H), 7.41-7.12 (m, 3.7H), 4.34(q, J ═ 7.1Hz, 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, 1.2Hz, 3H).

3-methyl-4, 5-dihydro-1H-benzo [ g ] indole and 7-bromo-3-methyl-4, 5-dihydro-1H-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-1H-benzo [ g]Indole-2-carboxylic acid ethyl ester (ratio of about 2: 1, 2.87mmol, 812mg) was dissolved in 30: 1 ethylene glycol/H ₂ To the mixture in O (25.0mL) was added sodium hydroxide (7.29mmol, 120mg), and the mixture was stirred at 150 ℃ for 4 hours. Then will beIt is cooled to room temperature and quenched with 1M NH ₄ Aqueous Cl (150mL) was quenched and the pH was adjusted to pH 3 with 6M HCl. The precipitate was collected by vacuum filtration and lyophilized for 16 hours to give 639mg of 3-methyl-4, 5-dihydro-1H-benzo [ g ]]Indole and 7-bromo-3-methyl-4, 5-dihydro-1H-benzo [ g]An inseparable mixture of indoles (ratio of about 2: 1, quantitative yield) was used without further purification in the subsequent synthetic steps.

(T-4) - [2- [ (4, 5-dihydro-3-methyl-7-bromo-2H-benzo [ g ] indol-2-ylidene-. kappa.N) - (2 ',6' -dimethyl-4 ' - (4- (perylenel) butoxy) phenyl) methyl ] -4, 5-dihydro-3-methyl-7-bromo-1H-benzo [ g ] indolino-. kappa.N ] difluoroboron (RLE-15)

To in CH ₂ Cl ₂ 3-methyl-4, 5-dihydro-1H-benzo [ g ] prepared as described above in (14.0mL)]Indole and 7-bromo-3-methyl-4, 5-dihydro-1H-benzo [ g]To a mixture of indole (300mg, ca. 1.42mmol) were added 15.3(0.568mmol, 267mg) and pTsOH. H ₂ O (0.057mmol, 7.00mg), and the reaction mixture was stirred at room temperature for 2 hours. Tetrachlorop-benzoquinone (0.568mmol, 140mg) was then added, and the mixture was stirred at room temperature for 15 minutes. Triethylamine (3.41mmol, 474. mu.L) was added, the mixture was stirred at room temperature for 30 minutes, and BF was then added ₃ ·OEt ₂ (5.11mmol, 631. mu.L) and the mixture was stirred at room temperature for 1 hour. It was then diluted with EtOAc (50.0mL), washed with 3M HCl (3X 50.0mL), dried (MgSO) ₄ ) And concentrated under reduced pressure. Flash chromatography (4: 1, toluene/hexane → 9: 1, toluene/hexane) afforded 105mg of RLE-15 (18% yield) as a dark blue/purple solid.

¹ H NMR (400MHz, chloroform-d) δ 8.78(d, J ═ 8.1Hz, 1H), 8.66(d, J ═ 8.8Hz, 1H), 8.27-8.13 (m, 4H), 7.96(d, J ═ 8.4Hz, 1H), 7.68(dd, J ═ 8.1, 4.4Hz, 2H), 7.59-7.37 (m, 7H), 7.31 (apparent t, J ═ 7.4Hz, 1H), 6.90(s, 2H), 3.21(t, J ═ 7.5Hz, 2H), 2.94-2.81 (m, 4H), 2.72(t, J ═ 7.2Hz, 2H), 2.57-2.48 (m, 4H), 2.33-2.22 (m, 2H), 2.18(s, 6.35H), 6.3.3 (d, 1H).

Example RLE-16

16.1 Synthesis:

compound 15.4A (methyl 3-oxo-3- (perylene-3-yl) propionate): a500 mL 3-neck round bottom flask was equipped with a stir bar and flushed with argon. To the flask was added AlCl ₃ (9.52mmol, 1.27g, followed by addition of anhydrous dichloromethane (160 mL.) the solution is stirred at room temperature and methyl 3-chloro-3-oxopropanoate (8.30mmol, 0.890mL), followed by perylene (7.92mmol, 1.99 g.) the reaction is stirred at room temperature under argon overnight the next morning, the flask is equipped with a finned air condenser and heated to 45 ℃ with a heating block and stirred at this temperature under argon for the entire weekend, another portion of methyl 3-chloro-3-oxopropanoate (8.30mmol, 0.890mL) is added and stirring is continued under argon at 45 ℃ overnight the reaction is quenched by addition of water (100mL) and 6N aqueous HCl (100mL) and diluted with dichloromethane (100mL), the layers are separated (emulsion) and the aqueous layer is extracted with DCM (2X 200mL, emulsion), then extracted with DCM (4X 100 mL). The organic layer was MgSO ₄ Dried, filtered, and concentrated in vacuo. The product was purified by flash chromatography on silica gel (100% DCM (3CV) → 1% EtOAc/DCM (0CV) → 1% EtOAc/DCM (3CV) → 10% EtOAc/DCM (8CV)) to give the product 1.905g (68% yield). Ms (apci): c ₂₄ H ₁₆ O ₃ The calculated value of (M + H) is 353; measured value: 353.

compound 15.4B (3- (perylen-3-yl) propionic acid): compound 42.1(3.10mmol, 1.091g) 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. 682mg (68% yield for 2 steps) were obtained. Ms (apci): c ₂₃ H ₁₆ O ₂ Calculated value of (M-H) 323; measured value: 323.

compound 15.4C (3- (peren-3-yl) propionic acid 4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) phenyl ester): compound 42.3 is prepared from compound 42.2(1.67mmol, 543mg) and 4- (4)4,5, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) phenol (2.51mmol, 553 mg). A40 mL screw cap vial was flushed with argon and charged with compound 42.2(1.67mmol, 543mg), 4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) phenol (2.51mmol, 553mg), DMAP (0.214mmol, 26mg), pTsOH.H ₂ O (0.193mmol, 36mg) and stir bar. The vial was sealed with a screw-cap septum, anhydrous DCM (4mL) was added, and the mixture was stirred to form a solution. DIC (0.642mmol, 0.100mL) was added to the stirred reaction and the mixture was stirred under argon overnight. The reaction mixture was diluted with ethyl acetate (150mL) and extracted with 3N aqueous HCl (25 mL). The organic layer was washed with saturated aqueous sodium bicarbonate (25mL), brine (15mL), MgSO ₄ Dried, filtered, and concentrated in vacuo. The material was purified by flash chromatography on silica gel (100% DCM (3CV) → 1% EtOAc/DCM (0CV) → 10% EtOAc/DCM (10CV)) to give the product after purification by flash chromatography on silica gel, 434mg (49% yield). Ms (apci): c ₃₅ H ₃₁ BO ₄ The calculated value of (M-H) is 525; measured value: 525.

(T-4) - [2- [ (4, 5-dihydro-3-methyl-7- ((4- (peryleneyl) butoxy) phenyl) methyl-2H-benzo [ g ] indol-2-ylidene-. kappa.N) - (2 ',6' -dimethyl-4 ' - (4- (peryleneyl) butoxy) phenyl) methyl ] -4, 5-dihydro-3-methyl-7- ((4- (peryleneyl) butoxy) phenyl) methyl-1H-benzo [ g ] indolinyl- -. kappa.N ] difluoroboron (RLE-16)

To a mixture of RLE-15(0.049mmol, 50.0mg) and 15.4(0.107mmol, 58.0mg) in a ratio of 6: 3: 1 in THF/toluene/water (1.00mL) PdCl was added ₂ (dppf) (0.002mmol, 1.80mg) and K ₂ CO ₃ (0.147mmol, 20.0mg) and the reaction mixture was heated to reflux for 16 h, then cooled to room temperature and quenched with 1M HCl (6.00 mL). CH for the mixture ₂ Cl ₂ Quench (3X 5.00mL) and dry the combined organics (MgSO) ₄ ) And concentrated under reduced pressure. Flash chromatography (toluene → 49: 1, toluene/EtOAc) afforded 26.0mg of RLE-16 (31% yield) as a blue solid.

¹ H NMR (400MHz, dichloromethane-d) ₂ )δ8.79(dd，J＝18.7，8.3Hz，2H)，8.30–8.13(m，8H)，8.00(d，J＝8.4Hz，2H)，7.83–7.38(m，18H)，7.37–7.05(m，6H)，6.92(s，2H)，3.21(td，J＝7.8，4.6Hz，4H)，2.98(t，J＝7.0Hz，2H)，2.91(t，J＝7.1Hz，2H)，2.78–2.70(m，4H)，2.58(dt，J＝15.1，7.0Hz，4H)，2.35–2.11(m，10H)，1.38(d，J＝2.7Hz，6H)。

Example 2.17 RLE-17

(T-4) - [2- [ (4, 5-dihydro-3-methyl-2H-benzo [ g ] indol-2-ylidene-. kappa.N) - (2 ',6' -dimethylphenyl) methyl ] -4, 5-dihydro-3-methyl-1H-benzo [ g ] indoxyl-. kappa.N ] difluoroboron and (T-4) - [2- [ (4, 5-dihydro-3-methyl-7-bromo-2H-benzo [ g ] indol-2-ylidene-. kappa.N) - (2 ',6' -dimethylphenyl) methyl ] -4, 5-dihydro-3-methyl-7-bromo-1H-benzo [ g ] indoxyl-. kappa.N ] difluoroboron (17.2).

To in CH ₂ Cl ₂ 3-methyl-4, 5-dihydro-1H-benzo [ g ] prepared as described above in (10.0mL)]Indole and 7-bromo-3-methyl-4, 5-dihydro-1H-benzo [ g]Indole (248mg, ca. 1.17mmol) and pTsOH. H ₂ O (0.039mmol, 5.00mg) in a mixture was added to CH ₂ Cl ₂ 2, 6-dimethylbenzaldehyde (0.391mmol, 52mg) (2.00mL), and the reaction mixture was stirred at room temperature for 1 hour. Tetrachlorop-benzoquinone (0.391mmol, 96.0mg) was then added, and the mixture was stirred at room temperature for 20 minutes. Triethylamine (2.34mmol, 326. mu.L) was added, the mixture was stirred at room temperature for 30 minutes, and BF was then added ₃ ·OEt ₂ (3.52mmol, 434. mu.L), and the mixture was stirred at room temperature for 1 hour. More triethylamine (1.17mmol, 163. mu.L) was added, and after stirring at room temperature for 10 minutes, BF was added ₃ ·OEt ₂ (1.76mmol, 217. mu.L), and the mixture was stirred at room temperature for another 30 minutes. The mixture was then diluted with EtOAc (50.0mL), washed with 3M HCl (3X 50.0mL), dried (MgSO) ₄ ) And concentrated under reduced pressure. Flash chromatography (1: 1, toluene/hexane) gave 133mg of (T-4) - [2- [ (4, 5-dihydro-3-methyl-2H-benzo [ g)]Indol-2-ylidene-kappa N) - (2 ',6' -dimethylphenyl) methyl]-4, 5-dihydro-3-methyl-1H-benzo [ g]Indolo-kappa N]Difluoro boron and (T-4) - [2- [ (4, 5-dihydro-3-methyl-7-bromo-2H-benzo [ g)]Indol-2-ylidene-kappa N) - (2 ',6' -dimethylphenyl) methyl]-4, 5-dihydro-3-methyl-7-bromo-1H-benzo [ g]Indolo-kappa N]Difluoroboron (ratio of about 2: 1), a dark blue/purple solid that was used without further purification in the subsequent synthetic steps.

(T-4) - [2- [ (4, 5-dihydro-3-methyl-7- ((4- (peryleneyl) butoxy) phenyl) methyl-2H-benzo [ g ] indol-2-ylidene-. kappa.N) - (2 ',6' -dimethylphenyl) methyl ] -4, 5-dihydro-3-methyl-7- ((4- (peryleneyl) butoxy) phenyl) methyl-1H-benzo [ g ] indolino-. kappa.N ] difluoroboron (RLE-17)

To (T-4) - [2- [ (4, 5-dihydro-3-methyl-7-bromo-2H-benzo [ g) prepared as described above]Indol-2-ylidene-kappa N) - (2 ',6' -dimethylphenyl) methyl]-4, 5-dihydro-3-methyl-7-bromo-1H-benzo [ g]Indolo-kappa N]A mixture of difluoride (133mg, about 0.194mmol) and 17.3(0.426mmol, 230mg) was mixed in a 6: 3: 1 in THF/toluene/water (4.00mL) PdCl was added ₂ (dppf) (0.010mmol, 7.00mg) and K ₂ CO ₃ (0.582mmol, 80.0mg) and the reaction mixture was heated to reflux for 16 h, then cooled to room temperature and quenched with 1M HCl (10.0 mL). CH for the mixture ₂ Cl ₂ (3X 10.0mL) and the combined organics were dried (MgSO ₄ ) And concentrated under reduced pressure. Flash chromatography (4: 1, toluene/hexane → toluene) afforded 51.0mg of RLE-17 (10% overall yield) as a dark blue/purple solid.

¹ H NMR (400MHz, dichloromethane-d) ₂ )δ8.90–8.71(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＝7.7Hz，2H)，3.09–2.84(m，4H)，2.75(t，J＝7.2Hz，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] cycloheptane [1,2-b ] pyrrole (18.1)

To a solution of 1-benzocycloheptane (10.0mmol, 1.46mL) in 3: 1H ₂ NH was added to a solution of O/EtOH (32.5mL) ₂ OH HCl (15.0mmol, 1.04g) and sodium acetate (25.0mmol, 2.05g) and the reaction mixture was stirred at 95 ℃ for 1 hour. It was then cooled to room temperature, filtered, washed with water (150mL), and lyophilized for 16 hours to give 1.64g of 6,7,8, 9-tetrahydro-5H-benzo [ 7]]Cyclohepten-5-one oxime (94% yield) was a colorless solid which was used without further purification in the subsequent synthesis steps.

To 6,7,8, 9-tetrahydro-5H-benzo [ 7] at room temperature]A solution of cyclohepten-5-one oxime (5.71mmol, 1.00g) in DMSO (9.00mL) was added KOH (17.1mmol, 959mg) and the reaction mixture was heated to 140 deg.C and then 1, 2-dichloroethane (11.4mmol, 897 μ L) in DMSO (2.00mL) was added by syringe pump over 3 hours. The mixture was then cooled to room temperature and quenched with 1M NH ₄ Aqueous Cl (30.0mL) and quenched with CH ₂ Cl ₂ (3X 30.0mL) was extracted. The combined organics were dried (MgSO) ₄ ) And concentrated under reduced pressure. Flash chromatography (hexane → 9: 1, hexane/EtOAc) afforded 262mg of compound 18.1 (25% yield) as a yellow solid.

¹ H NMR (400MHz, chloroform-d) δ 8.18(br s, 1H), 7.34(dd, J ═ 7.8, 1.3Hz, 1H), 7.25 to 7.19(m, 1H), 7.16(dd, J ═ 7.6, 1.6Hz, 1H), 7.13 to 7.07(m, 1H), 6.84(t, J ═ 2.8Hz, 1H), 6.17(t, J ═ 2.8Hz, 1H), 2.91(t, J ═ 6.8Hz, 2H), 2.86 to 2.80(m, 2H), 2.07 to 1.98(m, 2H); ¹³ c NMR (101MHz, chloroform-d) delta 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-18. lambda ⁴ ,19λ ⁴ -benzo [3',4']Cycloheptane [1', 2': 4,5]Pyrrolo [1,2-c]Benzo [3',4']Cycloheptane [1', 2': 4,5]Pyrrolo [2, 1-f)][1,3,2]Diazaborane-9-yl)-3, 5-difluorophenol (18.2)

To compound 18.1(1.36mmol, 250mg) and 2, 6-difluoro-4-hydroxybenzaldehyde (0.650mmol, 103mg) in CH ₂ Cl ₂ (13.5mL) to the solution was added pTsOH. H ₂ O (0.065mmol, 8mg), and the reaction mixture was stirred at room temperature for 1 hour. DDQ (0.780mmol, 177mg) was then added, and the mixture was stirred at room temperature for 1 hour. Triethylamine (3.90mmol, 542. mu.L) was added, the mixture was stirred at room temperature for 1 hour, and BF was then added ₃ ·OEt ₂ (5.85mmol, 722. mu.L) and the mixture was stirred at room temperature for 1 hour. More triethylamine (3.90mmol, 542. mu.L) was added and after stirring for 30 min at room temperature BF was added ₃ ·OEt ₂ (5.85mmol, 722. mu.L) and the mixture was stirred at room temperature for another 1 hour. It was then diluted with EtOAc (30.0mL), washed with 3M HCl (3X 30.0mL), and dried (MgSO) ₄ ) And concentrated under reduced pressure. Flash chromatography (toluene → 19: 1, toluene/EtOAc) afforded 149mg of compound 18.2 (42% yield) as a blue solid.

¹ H NMR(400MHz，DMSO-d ₆ )δ7.73(d，J＝7.4Hz，1H)，7.31–7.14(m，4H)，6.71(s，1H)，6.62(d，J＝10.0Hz，1H)，2.47–2.40(m，2H)，2.28–2.04(m，2H)，1.90–1.83(m，3H)。

4- (19, 19-difluoro-6, 7,11,12,13, 19-hexahydro-5H-18. lambda ⁴ ,19λ ⁴ -benzo [3',4']Cycloheptane [1', 2': 4,5]Pyrrolo [1,2-c]Benzo [3',4']Cycloheptane [1', 2': 4,5]Pyrrolo [2,1-f][1,3,2]Diazaboron-9-yl) -3, 5-difluorophenyl-4- (tris (trifluoromethyl) perylene-3-yl) butanoate (RLE-18)

To a mixture of 18.2(0.091mmol, 50mg), 4- (4,9, 10-tris (trifluoromethyl) perylenel-3-yl) butanoic acid (0.099mmol, 54mg) and DMAP pTsOH salt (0.091mmol, 27mg) in CH ₂ Cl ₂ (0.50mL) DIC (0.364mmol, 57. mu.L) was added and the reaction mixture was stirred at room temperature for 1 hour. However, the device is not suitable for use in a kitchenThe reaction mixture was then filtered through celite and concentrated under reduced pressure. Flash chromatography (4: 1, toluene/hexane → toluene) afforded 77mg of RLE-18 (78% yield) as a dark purple solid.

¹ H NMR (400MHz, 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) butanoic acid 3, 5-dichloro-4-formylphenyl ester (19.1)

To 2, 6-dichloro-4-hydroxybenzaldehyde (0.335mmol, 64mg), 4- (tris (trifluoromethyl) perylen-3-yl) butanoic acid (0.369mmol, 200mg) and DMAP pTsOH salt (0.034mmol, 10mg) in CH ₂ Cl ₂ To a solution in (1.68mL) was added DIC (1.34mmol, 210. mu.L), 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) afforded 187mg of compound 19.1 (78% yield) as a yellow solid.

¹ H NMR (400MHz, chloroform-d) delta 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).

3, 5-dichloro-4- (19, 19-difluoro-6, 7,11,12,13, 19-hexahydro-5H-18. lambda ⁴ ,19λ ⁴ -benzo [3',4']Cycloheptane [1', 2': 4,5]Pyrrolo [1,2-c]Benzo [3',4']Cycloheptane [1', 2': 4,5]Pyrrolo [2,1-f][1,3,2]Diazaborane-9-yl) phenyl 4- (tris (trifluoromethyl) perylene-3-yl) butanoate (RLE-19)

To compound 19.1(0.461mmol, 84mg) and compound 18.1(0.210mmol, 150mg) in CH ₂ Cl ₂ (4.50mL) to the solution was added pTsOH. H ₂ O (0.021mmol, 3mg), andand the reaction mixture was stirred at room temperature for 1 hour. DDQ (0.252mmol, 57mg) was then added, and the mixture was stirred at room temperature for 1 hour. Triethylamine (1.26mmol, 175. mu.L) was added, the mixture was stirred at room temperature for 1 hour, and BF was then added ₃ ·OEt ₂ (1.89mmol, 233. mu.L), and the mixture was stirred at room temperature for 2 hours. It was then diluted with EtOAc (30.0mL), washed with 3M HCl (3X 30.0mL), dried (MgSO) ₄ ) And concentrated under reduced pressure. Flash chromatography (4: 1 toluene/hexane → toluene) afforded 106mg of RLE-19 (45% yield) as a purple solid.

¹ H NMR (400MHz, dichloromethane-d) ₂ )δ8.61–7.60(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) butanoyl chloride (20.1)

To 4- (tris (trifluoromethyl) perylene-3-yl) butyric acid (0.500mmol, 271mg) in CH ₂ Cl ₂ To a solution in (2.50mL) was added DMF (1 drop) and oxalyl chloride (1.00mmol, 86 μ L), and the reaction mixture was stirred at room temperature for 1.5 hours. All volatiles were removed under reduced pressure to give 252mg of compound 20.1 (90% yield) as a yellow/brown solid. The material is of sufficient purity to be used directly in subsequent synthetic steps.

6, 6-difluoro-13, 15-dimethyl-14- (3- (4,9, 10-tris (trifluoromethyl) perylen-3-yl) propyl) -12, 16-dihydro-6H-5 λ ⁴ ,6λ ⁴ -indeno [2', 1': 4,5]Pyrrolo [1,2-c ] s]Indeno [2', 1': 4,5]Pyrrolo [2,1-f][1,3,2]Diazaborane (RLE-20)

To compound 20.1(0.250mmol, 140mg) in CH at room temperature ₂ Cl ₂ (0.50mL) to the solution was added 3-methyl-1, 4-dihydroindeno [1,2-b ]]Pyrrole (0.550mmol, 93mg) in CH ₂ Cl ₂ (0.75mL), and the reaction mixture is stirred at room temperature for 2 hours, after which a second portion of 3-methyl-1, 4-dihydroindeno [1,2-b ] is added]Pyrrole (0.270mmol, 45mg) and the mixture stirred for another 1 h. Triethylamine (1.50mmol, 208. mu.L) was added, the mixture was stirred at room temperature for 30 minutes, and BF was then added ₃ ·OEt ₂ (2.25mmol, 278. mu.L) and the mixture was stirred at room temperature for 16 hours. It was then diluted with EtOAc (10.0mL), washed with 3M HCl (3X 10.0mL), dried (MgSO) ₄ ) And concentrated under reduced pressure. Flash chromatography (7: 3 hexane/toluene → toluene) afforded 29mg of RLE-20 (13% yield) as a purple solid.

EXAMPLE 3 production of Filter layer

The glass substrate is prepared in essentially the following manner. A 1.1mm thick glass substrate measuring 1 inch x 1 inch was cut to size. The glass substrates were then washed with detergent and Deionized (DI) water, rinsed with fresh DI water, and sonicated for about 1 hour. The glass was then immersed in isopropyl alcohol (IPA) and sonicated for about 1 hour. The glass substrate was then immersed in acetone and sonicated for about 1 hour. The glass was then removed from the acetone bath and dried with nitrogen at room temperature.

A 20 wt% solution of poly (methyl methacrylate) (PMMA) (average m.w.120,000 by GPC, available from millipore sigma, Burlington, MA, USA) copolymer in cyclopentanone (purity 99.9%) was prepared. The prepared copolymer was stirred at 40 ℃ overnight. [ PMMA ] CAS: 9011-14-7; [ cyclopentanone ] CAS: 120-92-3

The 20% PMMA solution (4g) prepared above was added to 3mg of the photoluminescent compound prepared as described above in a sealed container and mixed for about 30 minutes. The PMMA/luminophore solution was then spin coated onto the prepared glass substrate at 1000RPM for 20 seconds, followed by spin coating at 500RPM for 5 seconds. The thickness of the resulting wet coating was about 10 μm. Prior to spin coating, the samples were covered with aluminum foil to prevent exposure of the samples to light. Three samples were prepared in this way each for emission/FWHM and quantum yield, respectively. The spin-coated sample was baked in a vacuum oven at 80 ℃ for 3 hours to evaporate the residual solvent.

A 1 inch x 1 inch sample was inserted into a Shimadzu, UV-3600 UV-VIS-NIR spectrophotometer (Shimadzu Instruments, inc., Columbia, MD, USA). All plant operations were carried out in a nitrogen-filled glove box. The resulting absorption/emission spectrum of PC-8 is shown in FIG. 1, and the resulting absorption/emission spectrum of PC-33 is shown in FIG. 2.

Fluorescence spectra of 1 inch x 1 inch film samples prepared as described above were determined using a fluorologo spectrofluorometer (Horiba Scientific, Edison, NJ, USA) with excitation wavelengths set to the respective maximum absorption wavelengths. The maximum emission and FWHM are shown in table 1.

The quantum yield of the 1 inch x 1 inch samples prepared as described above was determined using a Quantarus-QY spectrophotometer (Hamamatsu inc., Campbell CA, USA) excited at the respective wavelengths of maximum absorption. The results are reported in table 1.

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

TABLE 1

Photostability test procedure:

using a dye concentration of 2X 10 ^-3 M to evaluate the light stability of the films. The PMMA film used for stabilization was the same as the film provided previously for all optical property measurements. 90.0mL of cyclopentanone was added to 30.0g of Polymethylmethacrylate (PMMA) polymer (Milipore-Sigma, St. Louis, Mo., USA) and stirred at 50 ℃ for several days. The resulting substrate solution was cast onto a previously cleaned (washed with soap and water) glass substrate (1 inch x 1 inch) by a casting machine set at a casting blade gap of 200 microns. After an additional 30 minutes of casting, the cast film was held under cover for 30 minutes. The cast glass surface was then placed on a hot plate and baked at 120 ℃ for about 20 minutes.

Blue LED light (supplier: immersed LED) with an emission peak at 465nm was used as the light source. A strip of blue LEDs was placed in a 1 "x 12" sized U-shaped channel and a commercially available diffuser film (not known by the supplier) was placed on top of the U-shaped channel to give a uniform light distribution. A membrane of size 1 "x 1" was placed on top of the diffuser. Average irradiance at the film was about 1.5mW/cm ² . Is disposed in the ambient environment.

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

The residual absorption measured after each exposure period divided by the absorption before exposure indicates the photostability of the film.

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

Depending on the amount of 20% PMMA solution. If X mL of PMMA solution is used to make the dye solution, 0.4X mg of additive is weighed and added to a 10mL vial. 100 microliters of toluene was added to dissolve the additives, and then the solution containing the additives was added to the PMMA dye solution. Sonication was carried out for 10 minutes.

(LA-57, from supplier: Adeka, Ni (AcAc)2, DABCO, all from sigma Aldrich)

The results are shown in the following table:

terms used in the present disclosure and the appended embodiments (e.g., bodies of the appended embodiments) are generally intended as "open" terms (e.g., the term "including" should be interpreted as "including but not limited to" having "should be interpreted as" having at least, "the term" includes "should be interpreted as" includes but is not limited to, "etc.). In addition, if a specific number of an element is introduced, this can be interpreted to mean at least the recited number, as may be dictated by the context (e.g., the mere expression "two recitations," without other modifiers, means at least two recitations of more than two recitations). As used in this disclosure, words and/or phrases that exhibit two or more alternative inflections should be understood to consider the possibility of including one of the terms, either of the terms, or both terms. For example, the phrase "a or B": will be understood to include the possibility of "A" or "B" or "A and B".

The use of the terms "a", "an", "the" and similar referents in the context of describing the invention (especially in the context of the following embodiments) is to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., "such as") provided herein, is intended merely to better illuminate the invention and does not pose a limitation on the scope of any embodiment. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention.

Groupings of alternative elements or embodiments disclosed herein are not to be construed as limitations. Each group member may be referenced and embodied individually or in any combination with other members of the group or other elements found herein. For reasons of convenience and/or patentability, one or more members of the intended group may be included in the group or deleted from the group. When any such inclusion or deletion occurs, the specification is to be considered as including the modified group so as to satisfy the written description of all markush groups used in the appended embodiments.

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

Claims

1. A photoluminescent complex represented by the formula:

A-(L--D) _1-3 ，

wherein each D is a donor chromophore that absorbs light having a first wavelength in the blue light range and releases excitation energy in response thereto, wherein the donor chromophore is:

wherein R is ⁸ 、R ¹⁰ And R ¹¹ Independently is H or CF ₃ ；

Wherein A is an acceptor chromophore comprising a dipyrromethene Boron (BODIPY) derivative, wherein the acceptor 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 is

Each L is a linking group; and is

Wherein the photoluminescence complex has an emission quantum yield greater than 80%.

2. The photoluminescent composite of claim 1, wherein:

a is as follows:

wherein each R' is independently H, -CH ₃ F, or CF ₃ ；

R' is-H, or a bond to L-D;

R ¹ and R ² Independently is H or-CH ₃ ；

R ³ And R ⁴ Independently H, F, Br, -CF ₃ Optionally with 1 or 2-CH ₃ 、-F、-CF ₃ A substituted phenyl, or a bond to L-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 or aromatic spiro-polycyclic radical, in which R is ^a Is C ₁ -C ₄ Alkyl, and wherein Ar is aryl or heteroaryl;

wherein R 'and R' are ³ Or R ⁴ Is a bond to L-D; and is

L is optionally substituted C ₄ -C ₇ Esters or C ₃ -C ₅ A ketoester.

3. A photoluminescent complex according to claim 1 or 2, wherein when X is spiro-cyclopentane.

4. A photoluminescent complex according to claim 1,2 or 3, wherein L is:

5. a photoluminescent complex according to claims 1,2 and 3, wherein L is:

6. the photoluminescent complex of claim 1,2,3,4, or 5, wherein the photoluminescent complex is:

7. a color conversion film, comprising:

a transparent substrate layer; and

a photoluminescent complex according to claim 1,2,3,4, 5, or 6 dispersed in the resin matrix.

8. The color conversion film of claim 7, further comprising a singlet oxygen quencher.

9. The color conversion film of claim 7, further comprising a free radical scavenger.

10. The color conversion film of claim 7, wherein the film has a thickness of between about 1 μ ι η to about 200 μ ι η.

11. The color conversion film of claim 7, wherein the film absorbs blue light having a wavelength of 400nm to 480nm and emits red light having a wavelength of 575nm to 650 nm.

12. The color conversion film of claim 11, wherein the film emits red light having a wavelength of 600nm to 650 nm.

13. The color conversion film of claim 7,8,9, 10, 11, or 12, wherein the film has a photostability of at least 80% after 165 hours exposure to blue light having a peak wavelength of 465 nm.

14. The color conversion film of claim 7,8,9, 10, 11,12, or 13, wherein the film has a photostability of at least 75% after 330 hours exposure to blue light having a peak wavelength of 465 nm.

15. A method of making a color conversion film according to claim 7,8,9, 10, 11,12,13, or 14, comprising:

applying the mixture to a surface of a transparent substrate;

wherein the mixture comprises a resin matrix dissolved in a solvent and the photoluminescent complex of claim 1,2,3,4, 5, or 6.

16. The method of claim 15, wherein the photoluminescent complex has an absorbance at a wavelength in the range of 400nm to 480nm and an emission at a wavelength in the range of 575nm to 650 nm.

17. The method of claim 15, wherein the mixture further comprises a radical scavenger dissolved in the solvent.

18. The method of claim 15, wherein the mixture further comprises a singlet oxygen quencher dissolved in the solvent.

19. A backlight unit comprising the color conversion film of claim 7,8,9, 10, 11,12,13, or 14.

20. A display device comprising the backlight unit of claim 19.