WO2020192271A1 - 一种荧光化合物、其制备方法及其用途 - Google Patents

一种荧光化合物、其制备方法及其用途 Download PDF

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WO2020192271A1
WO2020192271A1 PCT/CN2020/073720 CN2020073720W WO2020192271A1 WO 2020192271 A1 WO2020192271 A1 WO 2020192271A1 CN 2020073720 W CN2020073720 W CN 2020073720W WO 2020192271 A1 WO2020192271 A1 WO 2020192271A1
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formula
compound
boronic acid
salt
group
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PCT/CN2020/073720
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French (fr)
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何静
李世红
刘渊豪
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南京中硼联康医疗科技有限公司
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Priority to EP20778856.3A priority Critical patent/EP3950675A4/en
Priority to JP2021532396A priority patent/JP7297066B2/ja
Publication of WO2020192271A1 publication Critical patent/WO2020192271A1/zh
Priority to US17/405,152 priority patent/US20210388005A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/027—Organoboranes and organoborohydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/025—Boronic and borinic acid compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C09B23/06—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups three >CH- groups, e.g. carbocyanines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C09B23/08—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups more than three >CH- groups, e.g. polycarbocyanines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
    • C09K2211/1055—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms with other heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1096—Heterocyclic compounds characterised by ligands containing other heteroatoms

Definitions

  • the invention relates to the field of chemical dyes, in particular to a fluorescent compound, its preparation method and its use.
  • Cyanine dyes are widely used in spectral sensitization, infrared laser dyes, optical disc recording media, LB due to their large molar extinction coefficient, good fluorescence performance, increased fluorescence efficiency after being combined with the matrix, and large tunable range of maximum absorption wavelength. Films, electrophotography, optical nonlinear materials, solar cells, trace metal ion detection, etc.
  • the near-infrared heptamethine cyanine dye whose maximum absorption and emission wavelength is in the near-infrared region of 600-900nm, has obvious advantages in the analysis of some samples.
  • the present invention provides a fluorescent compound, a preparation method and use thereof.
  • the fluorescent compound can be used as a fluorescent dye, and its excitation wavelength is in the near-infrared region around 800 nm.
  • a fluorescent compound represented by formula I or a salt thereof, or an enantiomer, diastereomer, tautomer, solvate, Polymorphs, the compound having the structure
  • m and n are each independently an integer of 0-10;
  • Y 1 and Y 2 are each independently selected from the following group: hydrogen, phenyl, hydroxyl, carboxyl, ester, boronic acid, boronic ester, one or A 3-7 membered ring substituted with a plurality of boronic acid groups or boronic acid ester groups, and at least one of Y 1 and Y 2 is a boron-containing group.
  • Y 1 and Y 2 are each independently selected from the following group: hydrogen, phenyl, boronic acid group, boronic acid ester group, And Y 1 and Y 2 are not hydrogen at the same time, and Y 1 and Y 2 are not phenyl at the same time.
  • n and n are each independently an integer of 0-5.
  • R 1 and R 2 are each independently a hydroxyl group, or together with the boron atom to which they are connected, represent a group that can be hydrolyzed into boronic acid; preferably, R 1 and R 2 are each independently a hydroxyl group, or with The boron atoms to which they are attached together form a 5- to 8-membered ring that can be hydrolyzed to boric acid.
  • -BR 1 R 2 is a borate group or a borate group.
  • the salt has the structure of formula II
  • M represents an anion that forms a salt with N in formula II.
  • M includes iodide, chloride, bromide, alkyl sulfonate, tetrafluoroborate, sulfate, nitrate, phosphate, or perchlorate, formate, acetate, phenylpropane Amino acid radical; preferably, M includes iodide ion, chloride ion, and bromide ion.
  • Y 1 and Y 2 are each independently hydrogen, phenyl, or And Y 1 and Y 2 are not hydrogen at the same time, and Y 1 and Y 2 are not phenyl at the same time.
  • n and n are each independently an integer of 0-5.
  • R 1 and R 2 are each independently a hydroxyl group, or together with the boron atom to which they are attached, represent a group that can be hydrolyzed into boric acid, preferably together with the boron atom to which they are attached to form a group that can be hydrolyzed into boric acid. 5- to 8-membered ring.
  • -BR 1 R 2 is a borate group or a borate group.
  • Y 1 is More preferably
  • -BR 1 R 2 is a borate group or a borate group.
  • B is 10 B.
  • B has a 10 B purity of ⁇ 95%.
  • m and Y 1 are defined as described in the first aspect.
  • Y 1 is
  • R 1 and R 2 are each independently a hydroxyl group, or together with the boron atom to which they are attached, represent a group that can be hydrolyzed into boric acid, preferably together with the boron atom to which they are attached to form a group that can be hydrolyzed into boric acid. 5- to 8-membered ring.
  • m is 0 or 1.
  • the step includes: (i) a compound of formula a reacts with a compound of formula b to obtain a compound of formula c
  • X is halogen
  • m and Y 1 are as defined in the first aspect.
  • X is chlorine, bromine or iodine.
  • the step (i) includes the step of mixing the compound of formula a and the compound of formula b in a first inert solvent, and the compound of formula c is obtained after the reaction.
  • step (i) is reacted under the protection of inert gas.
  • step (i) is reacted at reflux temperature.
  • the compound of formula a and the compound of formula b are reacted under microwave conditions.
  • step (i) after the step (i), it further includes the step: (ii) the compound of formula c, the compound of formula c-1 and the compound of formula d are reacted to obtain a compound of formula I, wherein Y 1 , m, n , Y 2 is defined as described in the first aspect;
  • the compound of formula c-1 is synthesized in the same way as the compound of formula c.
  • the compound of formula c-1 is the same as the compound of formula c.
  • Y 1 and Y 2 are each independently selected from the following group: hydrogen, phenyl, boronic acid group, boronic acid ester group, And Y 1 and Y 2 are not hydrogen at the same time, and Y 1 and Y 2 are not phenyl at the same time.
  • n and n are each independently an integer of 0-5.
  • R 1 and R 2 are each independently a hydroxyl group, or together with the boron atom to which they are connected, represent a group that can be hydrolyzed to boric acid.
  • -BR 1 R 2 is a borate group or a borate group.
  • Y 2 Y 1 .
  • Y 2 is phenyl
  • the step (ii) further includes the step of mixing the compound of formula c and the compound of formula d in a second inert solvent, and the compound of formula I is obtained after the reaction.
  • step (ii) is reacted under the protection of inert gas.
  • step (ii) is reacted at a temperature of 30-100°C.
  • step (ii) further includes the step of adding a base to the second inert solvent.
  • the base is an alkali metal salt or an alkali metal hydride, wherein the alkali metal includes lithium, sodium, potassium, calcium, magnesium, and cesium.
  • the alkali metal salt includes: alkali metal hydroxide and alkali metal organic acid salt.
  • the first inert solvent and the second inert solvent are each independently selected from the following group: methanol, ethanol, isopropanol, ethylene glycol, N-methylpyrrolidone, dimethyl sulfoxide, Tetrahydrofuran, toluene, benzene, dichloromethane, chloroform, tetrachloromethane, 1,2-dichloroethane, acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, two Oxane, amine ether, or a combination thereof.
  • a fluorescent compound as described in the first aspect of the present invention or a salt, enantiomer, diastereomer, tautomer, solvate or polymorph thereof Types as fluorescent dyes.
  • Fig. 1 is a fluorescence spectrum of compound I-1 in Example 4 at room temperature.
  • Figure 2 is the fluorescence spectrum of compound 1-2 in Example 4 at room temperature.
  • Figure 3 is the near-infrared absorption spectra of compounds I-1 and I-2 in Example 4 in ethanol solution.
  • B refers to boron element, including radioactive and non-radioactive boron elements, preferably 10 B;
  • boronic acid group refers to -B(OH) 2 group.
  • the "3-7 membered ring” is a saturated or unsaturated carbocyclic or heteroatom-containing ring containing 3-7 carbon atoms, preferably an aromatic ring.
  • the "boron-containing group” refers to a group containing a B atom as described in this specification.
  • optional or “optionally” means that the event or condition described later may or may not occur, and the description includes both occurrence and non-occurrence of the event or condition.
  • optionally substituted aryl group means that the aryl group is substituted or unsubstituted, and the description includes both substituted aryl groups and unsubstituted aryl groups.
  • Steps refer to compounds that consist of the same atoms and are bonded by the same bonds, but have different three-dimensional structures.
  • the present invention will cover various stereoisomers and mixtures thereof.
  • the compound of the present invention contains an olefinic double bond, unless otherwise specified, the compound of the present invention is intended to include E- and Z-geometric isomers.
  • Tautomer refers to an isomer formed by transferring a proton from one atom of a molecule to another atom of the same molecule. All tautomeric forms of the compounds of the present invention will also be included in the scope of the present invention.
  • the compounds of the present invention or their salts may contain one or more chiral carbon atoms, and therefore can produce enantiomers, diastereomers and other stereoisomeric forms.
  • Each chiral carbon atom can be defined as (R)- or (S)- based on stereochemistry.
  • the present invention is intended to include all possible isomers, as well as their racemates and optically pure forms.
  • racemates, diastereomers or enantiomers can be selected as raw materials or intermediates.
  • Optically active isomers can be prepared using chiral synthons or chiral reagents, or resolved using conventional techniques, such as crystallization and chiral chromatography.
  • salt includes acid addition salts and base addition salts.
  • acid addition salt refers to a salt formed with an inorganic acid or an organic acid that can retain the biological effectiveness of the free base without other side effects.
  • Inorganic acid salts include, but are not limited to, hydrochloride, hydrobromide, sulfate, nitrate, phosphate, etc.; organic acid salts include, but are not limited to, formate, acetate, and 2,2-dichloroacetate , Trifluoroacetate, propionate, caproate, caprylate, caprate, undecylenate, glycolate, gluconate, lactate, sebacate, hexanoate Acid salt, glutarate, malonate, oxalate, maleate, succinate, fumarate, tartrate, citrate, palmitate, stearate, oleate , Cinnamate, laurate, malate, glutamate, pyroglutamate, as
  • Base addition salt refers to a salt that can be formed with an inorganic base or an organic base.
  • Salts derived from inorganic bases include, but are not limited to, sodium, potassium, lithium, ammonium, calcium, magnesium, iron, zinc, copper, manganese, aluminum, and the like.
  • Preferred inorganic salts are ammonium, sodium, potassium, calcium and magnesium salts.
  • Salts derived from organic bases include but are not limited to the following salts: primary amines, secondary amines and tertiary amines, substituted amines, including natural substituted amines, cyclic amines and basic ion exchange resins , Such as ammonia, isopropylamine, trimethylamine, diethylamine, triethylamine, tripropylamine, ethanolamine, diethanolamine, triethanolamine, dimethylethanolamine, 2-dimethylaminoethanol, 2-diethylaminoethanol, bicyclic Hexylamine, lysine, arginine, histidine, caffeine, procaine, choline, betaine, ethylenediamine, glucosamine, methylglucamine, theobromine, purine, piperazine, piperazine Pyridine, N-ethylpiperidine, polyamine resin, etc.
  • Preferred organic bases include isopropylamine, diethylamine, ethanolamine, trimethylamine
  • Polymorphs refer to different solid crystalline phases produced by the presence of two or more different molecular arrangements in certain compounds of the present invention in a solid state. Certain compounds of the present invention may exist in more than one crystal form, and the present invention is intended to include various crystal forms and mixtures thereof. Generally, crystallization will produce solvates of the compounds of the invention.
  • solvate as used in the present invention refers to an aggregate comprising one or more molecules of the compound of the present invention and one or more solvent molecules.
  • the solvent may be water, and the solvate in this case is a hydrate. Alternatively, the solvent may be an organic solvent.
  • the compounds of the present invention may exist as hydrates, including monohydrate, dihydrate, hemihydrate, sesquihydrate, trihydrate, tetrahydrate, etc., and corresponding solvated forms.
  • the compound of the present invention can form a real solvate, but in some cases, it can also retain only the indeterminate water or a mixture of water and part of the indeterminate solvent.
  • the compound of the present invention can be reacted in a solvent or precipitated or crystallized from the solvent. Solvates of the compounds of the present invention are also included in the scope of the present invention.
  • the present invention provides a method for preparing compounds of formula I and formula II.
  • the method includes the step of using a compound of formula c, which has the structure
  • m and Y 1 are as described in the first aspect of the present invention.
  • Y 1 is More preferably
  • the steps include: (i) a compound of formula a reacts with a compound of formula b to obtain a compound of formula c
  • X is halogen, and preferably X is chlorine, bromine or iodine.
  • the step (i) includes the step of mixing a compound of formula a and a compound of formula b in a first inert solvent, and obtaining a compound of formula c after the reaction.
  • the step (i) is reacted under the protection of inert gas.
  • the step (i) is reacted at reflux temperature.
  • the first inert solvent is not particularly limited, and is preferably selected from the following group: methanol, ethanol, isopropanol, ethylene glycol, N-methylpyrrolidone, dimethyl sulfoxide, tetrahydrofuran, toluene, benzene, dichloride Methane, chloroform, tetrachloromethane, 1,2-dichloroethane, acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, dioxane, amine ether, or Its composition.
  • the step further includes the step: (ii) a compound of formula c, a compound of formula c-1 and a compound of formula d are reacted to obtain a compound of formula I or a compound of formula II
  • the synthesis method of the compound of formula c-1 is the same as the synthesis method of the compound of formula c
  • the synthesis method of the compound of formula II includes the synthesis method of the compound of formula I
  • m, n, Y 1 , and Y 2 are as defined in the present invention
  • the structure of the compound of formula c-1 and the compound of formula c may be the same or different.
  • Y 1 is Y 2 is phenyl; more preferably, Y 1 is Y 2 is phenyl.
  • R 1 and R 2 are each independently a hydroxyl group, or together with the boron atom to which they are connected, represent a group that can be hydrolyzed into a boric acid.
  • -BR 1 R 2 is a borate group or a borate group.
  • the step (ii) is reacted in a second inert solvent, preferably under the protection of an inert gas.
  • the reaction conditions of (ii) are not particularly limited.
  • the step (ii) is reacted at a temperature of 30-100°C.
  • the step (ii) further includes the step of adding a base to the second inert solvent.
  • the base is not particularly limited.
  • the base is an alkali metal salt or an alkali metal hydride, wherein the alkali metal includes lithium, sodium, potassium, calcium, magnesium, and cesium.
  • the alkali metal salt includes: alkali metal hydroxide and alkali metal organic acid salt.
  • the second inert solvent is also not particularly limited, and is preferably selected from the following group: methanol, ethanol, isopropanol, ethylene glycol, N-methylpyrrolidone, dimethyl sulfoxide, tetrahydrofuran, toluene, benzene, Chloroform, chloroform, tetrachloromethane, 1,2-dichloroethane, acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, dioxane, amine ether, Or a combination thereof.
  • step (ii) when the structure of the compound of formula c-1 and the compound of formula c are the same, it is also possible to obtain two or three compounds of formula I and formula II with different structures at the same time, and such situations should also be included in the technical scheme of this application. For example, in Example 4 in this application, compounds I-1 and I-2 were obtained at the same time.
  • the reaction temperature can be appropriately selected due to the solvent, starting materials, reagents, etc.
  • the reaction time can also be appropriately selected due to the reaction temperature, solvent, starting materials, reagents, and the like.
  • the target compound can be separated and purified from the reaction system according to common methods, such as filtration, extraction, recrystallization, washing, silica gel column chromatography and other methods. Without affecting the next step of the reaction, the target compound can also go directly to the next step without separation and purification.
  • the N-substituent side chain is an important part of the dye molecular structure.
  • the light stability and fluorescence activity of the dye molecules obtained by using different substituents are very different. Therefore, it is very important to choose the appropriate substituent side chain.
  • the inventor found a class of fluorescent compounds with the structures of Formula I and Formula II, which have high fluorescence intensity and high sensitivity, and completed the present invention on this basis.

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Abstract

一种如通式I所示的荧光化合物，或其盐、对映异构体、非对映异构体、互变异构体、溶剂化物或多晶型物，具有结构（I）；其中，m、n各自独立地为0-10的整数；Y 1、Y 2各自独立地选自下组：氢、苯基、羟基、羧基、酯基、硼酸基、硼酸酯基、一个或多个硼酸基或硼酸酯基取代的3-7元环，且Y 1和Y 2至少一个为含硼的基团。所述化合物具有高荧光强度、高灵敏度的特点。

Description

一种荧光化合物、其制备方法及其用途 技术领域
本发明涉及化学染料领域，尤其是一种荧光化合物、其制备方法及其用途。
背景技术
菁类染料由于具有摩尔消光系数大、荧光性能良好、与基质结合后荧光效率增大、最大吸收波长可调谐范围大，使其被广泛应用于光谱增感、红外激光染料、光盘记录介质、LB膜、电子照相、光学非线性材料、太阳能电池、痕量金属离子检测等方面。
尤其是近红外七甲川菁染料，其最大吸收和发射波长在600-900nm的近红外区，在一些样品分析中有着明显的优越性。
发明内容
本发明提供了一种荧光化合物、其制备方法及其用途，所述荧光化合物可以作为荧光染料，其激发波长位于800nm左右的近红外区。
在本发明的第一方面，提供了一种如通式I所示的荧光化合物，或其盐，或其对映异构体、非对映异构体、互变异构体、溶剂化物、多晶型物，所述化合物具有结构
Figure PCTCN2020073720-appb-000001
其中，m、n各自独立地为0-10的整数；Y 1、Y 2各自独立地选自下组：氢、苯基、羟基、羧基、酯基、硼酸基、硼酸酯基、一个或多个硼酸基或硼酸酯基取代的3-7元环，且Y 1和Y 2至少一个为含硼的基团。
在另一优选例中，Y 1、Y 2各自独立地选自下组：氢、苯基、硼酸基、硼酸酯基、
Figure PCTCN2020073720-appb-000002
且Y 1和Y 2不同时为氢，且Y 1和Y 2不同时为苯基。
在另一优选例中，m、n各自独立地为0-5的整数。
在另一优选例中，m＝n；更优选地，m＝n＝0或m＝n＝1。
在另一优选例中，R 1、R 2各自独立地为羟基，或与它们连接的硼原子一起代表可水解为硼酸的基团；优选地R 1、R 2各自独立地为羟基，或与它们连接的硼原子一起形成可水解为硼酸的5至8元环。
在另一优选例中，-BR 1R 2为硼酸酯基或硼酸基。
在另一优选例中，其盐具有式II结构
Figure PCTCN2020073720-appb-000003
其中，M表示与式II中的N形成盐的阴离子。
在另一优选例中，M包括碘离子、氯离子、溴离子、烷基磺酸根、四氟硼酸根、硫酸根、硝酸根、磷酸根、或高氯酸根、甲酸根、乙酸根、苯丙氨酸根；优选地，M包括碘离子、氯离子、溴离子。
在另一优选例中，Y 1、Y 2各自独立地为氢、苯基、或
Figure PCTCN2020073720-appb-000004
且Y 1和Y 2不同时为氢，且Y 1和Y 2不同时为苯基。
在另一优选例中，m、n各自独立地为0-5的整数。
在另一优选例中，m＝n；更优选地，m＝n＝0或m＝n＝1。
在另一优选例中，R 1、R 2各自独立地为羟基，或与它们连接的硼原子一起代表可水解为硼酸的基团，优选地与它们连接的硼原子一起形成可水解为硼酸的5至8元环。
在另一优选例中，-BR 1R 2为硼酸酯基或硼酸基。
在另一优选例中，m＝n＝1，Y 2为苯基。
在另一优选例中，Y 1为
Figure PCTCN2020073720-appb-000005
更优选为
Figure PCTCN2020073720-appb-000006
在另一优选例中，-BR 1R 2为硼酸酯基或硼酸基。
在另一优选例中，B为 10B。
在另一优选例中，B具有≥95％的 10B纯度。
在本发明的第二方面，提供了一种如第一方面所述的化合物的制备方法，所述方法包括使用式c化合物的步骤，所述式c化合物具有结构
Figure PCTCN2020073720-appb-000007
其中，m、Y 1的定义如第一方面所述。
在另一优选例中，m为0-5的正整数；Y 1为
Figure PCTCN2020073720-appb-000008
在另一优选例中，Y 1为
Figure PCTCN2020073720-appb-000009
在另一优选例中，R 1、R 2各自独立地为羟基，或与它们连接的硼原子一起代表可水解为硼酸的基团，优选地与它们连接的硼原子一起形成可水解为硼酸的5至8元环。
在另一优选例中，m为0或1。
在另一优选例中，所述步骤包括：(i)式a化合物与式b化合物反应，得到式c化合物
Figure PCTCN2020073720-appb-000010
其中，X为卤素，m、Y 1的定义如第一方面所述。
在另一优选例中，X为氯、溴或碘。
在另一优选例中，所述步骤(i)包括步骤：将式a化合物、式b化合物在第一惰性溶剂中混合，反应后得到式c化合物。
在另一优选例中，所述步骤(i)在惰性气体保护下反应。
在另一优选例中，所述步骤(i)在回流温度下反应。
在另一优选例中，所述式a化合物、式b化合物在微波条件下反应。
在另一优选例中，在所述步骤(i)之后，还包括步骤：(ii)式c化合物、式c-1化合物与式d化合物反应，得到式I化合物，其中Y 1、m、n、Y 2的定义如第一方面所述；
Figure PCTCN2020073720-appb-000011
式c化合物与式d化合物反应，得到式I化合物
Figure PCTCN2020073720-appb-000012
在另一优选例中，所述式c-1化合物与式c化合物的合成方法相同。
在另一优选例中，式c-1化合物与式c化合物相同。
在另一优选例中，Y 1、Y 2各自独立地选自下组：氢、苯基、硼酸基、硼酸酯基、
Figure PCTCN2020073720-appb-000013
且Y 1和Y 2不同时为氢，且Y 1和Y 2不同时为苯基。
在另一优选例中，m、n各自独立地为0-5的整数。
在另一优选例中，m＝n；更优选地，m＝n＝0或m＝n＝1。
在另一优选例中，R 1、R 2各自独立地为羟基，或与它们连接的硼原子一起代表可水解为硼酸的基团。
在另一优选例中，-BR 1R 2为硼酸酯基或硼酸基。
在另一优选例中，Y 2＝Y 1。
在另一优选例中，Y 1为
Figure PCTCN2020073720-appb-000014
Y 2＝Y 1。
在另一优选例中，Y 1为
Figure PCTCN2020073720-appb-000015
Y 2＝Y 1。
在另一优选例中，Y 2为苯基。
在另一优选例中，所述步骤(ii)还包括步骤：将式c化合物、式d化合物在第二惰性溶剂中混合，反应后得到式I化合物。
在另一优选例中，所述步骤(ii)在惰性气体保护下反应。
在另一优选例中，所述步骤(ii)在30-100℃温度下反应。
在另一优选例中，所述步骤(ii)还包括在第二惰性溶剂中加入碱的步骤。
在另一优选例中，所述碱为碱金属盐或碱金属氢化物，其中所述碱金属包括：锂、钠、钾、钙、镁、铯。
在另一优选例中，所述碱金属盐包括：碱金属的氢氧化物、碱金属的有机酸盐。
在另一优选例中，所述第一惰性溶剂、第二惰性溶剂各自独立地选自下组：甲醇、乙醇、异丙醇、乙二醇、N-甲基吡咯烷酮、二甲基亚砜、四氢呋喃、甲苯、苯、二氯甲烷、三氯甲烷、四氯甲烷、1,2-二氯乙烷、乙腈、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二氧六环、胺醚，或其组合物。
在另一优选例中，式c化合物结构为
Figure PCTCN2020073720-appb-000016
在本发明的第三方面提供了一种如本发明第一方面所述荧光化合物，或其盐、对映异构体、非对映异构体、互变异构体、溶剂化物或多晶型物作为荧光染料的用途。
应理解，在本发明范围内，本发明的上述各技术特征和在下文(如实施例)中具体描述的 各技术特征之间都可以互相组合，从而构成新的或优选的技术方案。限于篇幅，在此不再一一累述。
附图说明
图1是实施例4中的化合物I-1在室温下的荧光图谱。
图2是实施例4中的化合物I-2在室温下的荧光图谱。
图3是实施例4中的化合物I-1、I-2在乙醇溶液中的近红外吸收光谱。
术语
除非另有定义，否则本文所有科技术语具有的涵义与权利要求主题所属领域技术人员通常理解的涵义相同。除非另有说明，本文全文引用的所有专利、专利申请、公开材料通过引用方式整体并入本文。
应理解，上述简述和下文的详述为示例性且仅用于解释，而不对本发明主题作任何限制。在本申请中，除非另有具体说明，否则使用单数时也包括复数。必须注意，除非文中另有清楚的说明，否则在本说明书和权利要求书中所用的单数形式包括所指事物的复数形式。还应注意，除非另有说明，否则所用“或”、“或者”表示“和/或”。此外，所用术语“包括”以及其它形式，例如“包含”、“含”和“含有”并非限制性。
本文所用的章节标题仅用于组织文章的目的，而不应被解释为对所述主题的限制。本申请中引用的所有文献或文献部分包括但不限于专利、专利申请、文章、书籍、操作手册和论文，均通过引用方式整体并入本文。
除前述以外，当用于本申请的说明书及权利要求书中时，除非另外特别指明，否则以下术语具有如下所示的含义。
在本申请中，“B”指硼元素，包括具有放射性和非放射性的硼元素，优选为 10B；“硼酸基”指-B(OH) 2基团。“3-7元环”为含有3-7个碳原子的饱和或不饱和的碳环或含杂原子的环，优选地为芳香环。“含硼的基团”是指本说明书中所述的含有B原子的基团。
在本申请中，“任选的”或“任选地”表示随后描述的事件或状况可能发生也可能不发生，且该描述同时包括该事件或状况发生和不发生的情况。例如，“任选地被取代的芳基”表示芳基被取代或未被取代，且该描述同时包括被取代的芳基与未被取代的芳基。
“立体异构体”是指由相同原子组成，通过相同的键键合，但具有不同三维结构的化合物。 本发明将涵盖各种立体异构体及其混合物。
当本发明的化合物中含有烯双键时，除非另有说明，否则本发明的化合物旨在包含E-和Z-几何异构体。
“互变异构体”是指质子从分子的一个原子转移至相同分子的另一个原子而形成的异构体。本发明的化合物的所有互变异构形式也将包含在本发明的范围内。
本发明的化合物或其盐可能含有一个或多个手性碳原子，且因此可产生对映异构体、非对映异构体及其它立体异构形式。每个手性碳原子可以基于立体化学而被定义为(R)-或(S)-。本发明旨在包括所有可能的异构体，以及其外消旋体和光学纯形式。本发明的化合物的制备可以选择外消旋体、非对映异构体或对映异构体作为原料或中间体。光学活性的异构体可以使用手性合成子或手性试剂来制备，或者使用常规技术进行拆分，例如采用结晶以及手性色谱等方法。
在本申请中，术语“盐”包括酸加成盐和碱加成盐。其中，“酸加成盐”是指能够保留游离碱的生物有效性而无其它副作用的，与无机酸或有机酸所形成的盐。无机酸盐包括但不限于盐酸盐、氢溴酸盐、硫酸盐、硝酸盐、磷酸盐等；有机酸盐包括但不限于甲酸盐、乙酸盐、2,2-二氯乙酸盐、三氟乙酸盐、丙酸盐、己酸盐、辛酸盐、癸酸盐、十一碳烯酸盐、乙醇酸盐、葡糖酸盐、乳酸盐、癸二酸盐、己二酸盐、戊二酸盐、丙二酸盐、草酸盐、马来酸盐、琥珀酸盐、富马酸盐、酒石酸盐、柠檬酸盐、棕榈酸盐、硬脂酸盐、油酸盐、肉桂酸盐、月桂酸盐、苹果酸盐、谷氨酸盐、焦谷氨酸盐、天冬氨酸盐、苯甲酸盐、甲磺酸盐、苯磺酸盐、对甲苯磺酸盐、海藻酸盐、抗坏血酸盐、水杨酸盐、4-氨基水杨酸盐、萘二磺酸盐等。“碱加成盐”是指能够与无机碱或有机碱所形成的盐。衍生自无机碱的盐包括但不限于钠盐、钾盐、锂盐、铵盐、钙盐、镁盐、铁盐、锌盐、铜盐、锰盐、铝盐等。优选的无机盐为铵盐、钠盐、钾盐、钙盐及镁盐。衍生自有机碱的盐包括但不限于以下的盐：伯胺类、仲胺类及叔胺类，被取代的胺类，包括天然的被取代胺类、环状胺类及碱性离子交换树脂，例如氨、异丙胺、三甲胺、二乙胺、三乙胺、三丙胺、乙醇胺、二乙醇胺、三乙醇胺、二甲基乙醇胺、2-二甲氨基乙醇、2-二乙氨基乙醇、二环己胺、赖氨酸、精氨酸、组氨酸、咖啡因、普鲁卡因、胆碱、甜菜碱、乙二胺、葡萄糖胺、甲基葡萄糖胺、可可碱、嘌呤、哌嗪、哌啶、N-乙基哌啶、聚胺树脂等。优选的有机碱包括异丙胺、二乙胺、乙醇胺、三甲胺、二环己基胺、胆碱及咖啡因。
“多晶型物”是指本发明的某些化合物在固体状态下由于存在两种或两种以上不同分子排列而产生的不同固体结晶相。本发明的某些化合物可以存在多于一种晶型，本发明旨在包括 各种晶型及其混合物。通常，结晶化作用会产生本发明化合物的溶剂化物。本发明中使用的术语“溶剂化物”是指包含一个或多个本发明化合物分子与一个或多个溶剂分子的聚集体。溶剂可以是水，该情况下的溶剂化物为水合物。或者，溶剂可以是有机溶剂。因此，本发明的化合物可以以水合物存在，包括单水合物、二水合物、半水合物、倍半水合物、三水合物、四水合物等，以及相应的溶剂化形式。本发明化合物可形成真实的溶剂化物，但在某些情况下，也可以仅保留不定的水或者水加上部分不定溶剂的混合物。本发明的化合物可以在溶剂中反应或者从溶剂中沉淀析出或结晶出来。本发明化合物的溶剂化物也包含在本发明的范围之内。
式I化合物的制备方法
本发明提供了一种式I、式II化合物的制备方法，所述方法包括使用式c化合物的步骤，所述式c化合物具有结构
Figure PCTCN2020073720-appb-000017
式c；
其中，m、Y 1的定义如本发明第一方面中所述。
优选地为0-5的整数，更优选地为0或1；优选地Y 1为
Figure PCTCN2020073720-appb-000018
更优选地为
Figure PCTCN2020073720-appb-000019
所述步骤包括：(i)式a化合物与式b化合物反应，得到式c化合物
Figure PCTCN2020073720-appb-000020
其中，X为卤素，优选的X为氯、溴或碘。
在一个优选的实施方式中，所述步骤(i)包括步骤：将式a化合物、式b化合物在第一惰性溶剂中混合，反应后得到式c化合物。优选地，所述步骤(i)在惰性气体保护下反应。优选地，所述步骤(i)在回流温度下反应。所述第一惰性溶剂没有特别的限制，优选地选自下组：甲醇、乙醇、异丙醇、乙二醇、N-甲基吡咯烷酮、二甲基亚砜、四氢呋喃、甲苯、苯、二氯 甲烷、三氯甲烷、四氯甲烷、1,2-二氯乙烷、乙腈、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二氧六环、胺醚，或其组合物。
在一个优选的实施方式中，所述步骤还包括步骤：(ii)式c化合物、式c-1化合物与式d化合物反应，得到式I化合物或式II化合物
Figure PCTCN2020073720-appb-000021
将式c化合物、式d化合物反应得到式I化合物
Figure PCTCN2020073720-appb-000022
其中，所述式c-1化合物的合成方法与式c化合物的合成方法相同，式II化合物的合成方法包括式I化合物的合成方法；m、n、Y 1、Y 2的定义如本发明第一方面所述。其中，式c-1化合物与式c化合物的结构可以相同也可以不同。在上述各个制备方法中，优选的Y 1为
Figure PCTCN2020073720-appb-000023
Y 2＝Y 1；更优选地，Y 1为
Figure PCTCN2020073720-appb-000024
Y 2＝Y 1。在一个优选的实施方式中，优选地m＝n＝0至5的整数；更优选地m＝n＝0或1。在一个优选的实施方式中，Y 1为
Figure PCTCN2020073720-appb-000025
Y 2为苯基；更优选地，Y 1为
Figure PCTCN2020073720-appb-000026
Y 2为苯基。其中，R 1、R 2各自独立地为羟基，或与它们连接的硼原子一起代表可水解为硼酸的基团，优选地-BR 1R 2为硼酸酯基或硼酸基。
所述步骤(ii)在第二惰性溶剂中反应，优选地在惰性气体保护下反应。所述(ii)的反应条件没有特别的限制，优选地，所述步骤(ii)在30-100℃温度下反应。在一个优选的实施方式中，所述步骤(ii)还包括在第二惰性溶剂中加入碱的步骤。所述的碱没有特别的限制，优选地所述碱为碱金属盐或碱金属氢化物，其中所述碱金属包括：锂、钠、钾、钙、镁、铯。优选 地，所述碱金属盐包括：碱金属的氢氧化物、碱金属的有机酸盐。所述第二惰性溶剂也没有特别的限制，优选地选自下组：甲醇、乙醇、异丙醇、乙二醇、N-甲基吡咯烷酮、二甲基亚砜、四氢呋喃、甲苯、苯、二氯甲烷、三氯甲烷、四氯甲烷、1,2-二氯乙烷、乙腈、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二氧六环、胺醚，或其组合物。
需要注意的是，根据本发明的制备式I、式II化合物方法，在一些实施方案中，在所述步骤(ii)中，在式c-1化合物与式c化合物的结构相同的情况下，也可以同时得到两个或三个不同结构的式I、式II化合物，这样的情况也应该包括在本申请的技术方案中。例如在本申请中的实施例4中，同时得到了化合物I-1和I-2。
各步骤的反应，反应温度可因溶剂、起始原料、试剂等适宜选择，反应时间也可因反应温度、溶剂、起始原料、试剂等适宜选择。各步骤反应结束后，目标化合物可按常用方法自反应体系中进行分离、提纯等步骤，如过滤、萃取、重结晶、洗涤、硅胶柱层析等方法。在不影响下一步反应的情况下，目标化合物也可不经过分离、纯化直接进入下一步反应。
具体实施方式
N-取代基侧链是染料分子结构的重要组成部分，使用不同的取代基得到的染料分子的光稳定性及荧光活性具有很大差异，因此选择合适的取代基侧链至关重要。本发明人经过广泛而深入地研究，发现了一类具有式I、式II结构的荧光化合物，所述化合物具有高荧光强度、高灵敏度，在此基础上，完成了本发明。
以下结合具体实施例，进一步说明本发明。需理解，以下的描述仅为本发明的最优选实施方式，而不应当被认为是对于本发明保护范围的限制。在充分理解本发明的基础上，下列实施例中未注明具体条件的实验方法，通常按照常规条件，或按照制造厂商所建议的条件，本领域技术人员可以对本发明的技术方案做出非本质的改动，这样的改动应当被视为包括于本发明的保护范围之中的。除非另外说明，否则百分比和份数是重量百分比和重量份数。
<实施例1>
准备干燥的三口瓶，进行氮气置换，保证各溶剂及原料无水。依次加入180ml的胺醚，搅拌加入3.3gNaH，及30g的3-甲基碘苯，搅拌至体系基本不冒泡。向体系内加入101g的硼酸正丁酯，氮气保护，降温至0℃以下。取375ml的叔丁基氯化镁，缓慢滴加到体系中，维持体系温度不高于15℃。滴加完毕后自然升温至室温，反应3h后，TLC监测反应完毕。向体系内加入1800ml叔丁醚：乙酸乙酯(1:1)的混合溶剂稀释，加水淬灭，淬灭过程中温度 不高于30℃。向体系中滴加6mol/L的盐酸调节pH至3-4，分液得到有机相，水洗4次有机相，最后用盐水洗涤，旋干得到粗品。通过石油醚：乙酸乙酯＝8:1的溶剂洗涤、过滤干燥得到15.7g的3-甲基苯硼酸，收率83.92％，纯度99.02％。
<实施例2>
向三口瓶中加入200ml干燥的CCl 4,9g的3-甲基苯硼酸，1.6g的过氧化苯甲酰，在氮气保护下搅拌升温至65℃，恒温5min，引发过氧化苯甲酰。分批加入11.64g的N-溴代琥珀酰亚胺，回流反应一夜后，降温至室温，搅拌片刻后过滤，用石油醚：乙酸乙酯＝8:1混合溶剂洗涤产品，得到13.5g的3-溴甲基苯硼酸，收率95.32％，纯度91.33％。
<实施例3>
向单口瓶中加入100ml干燥的甲苯，9.07g的2,3,3-二甲基-三氢吲哚，13.5g的3-溴甲基苯硼酸，氮气保护下，回流反应过夜，降温至室温后，过滤得到紫红色固体，乙酸乙酯洗去杂质，干燥后得到15g的3-溴甲基苯硼酸吲哚季铵盐，收率89.44％，纯度97.33％。
<实施例4>
向单口瓶中加入300ml无水乙醇，6.47g的3-溴甲基苯硼酸吲哚季铵盐，2-氯-3-羟次甲基环己烯醛，0.15g的乙酸钠，在70℃下反应1h，旋干溶剂，通过柱层析分离，得到荧光化合物I-1和I-2。荧光化合物I-1在790nm的激发波长下的最大荧光发射峰在808nm，在乙醇溶液中的近红外吸收峰在785nm。荧光化合物I-2在790nm的激发波长下的最大荧光发射峰在811nm，在乙醇溶液中的近红外吸收峰在788nm。
化合物I-1    1H NMR(500MHz,DMSO-D6):
δ＝1.72-1.74(14H,4CH 3,CH 2,m),2.53-2.54(4H,2CH 2,m),3.17(4H,s),4.04(2H,s,br),5.54(4H,s,br),6.38(2H,CH,d＝14.0),7.26-7.36(6H,m,ArCH),7.39(2H,ArCH,d＝2.8),7.66-7.73(6H,ArCH,m),8.01(2H,ArCH,s),8.24(2H,CH,d＝14.0)。
化合物I-2    1H NMR(500MHz,DMSO-D6):
δ＝1.66-1.73(14H,4CH 3,CH2,m),2.52-2.56(4H,2CH 2,m),3.12(2H,s),3.61(2H,s),5.50(4H,s,br),6.41(2H,m,CH),7.31-7.41(13H,m,ArCH),7.62-7.73(4H,ArCH,m),8.24-8.28(2H,CH,m)。
Figure PCTCN2020073720-appb-000027
在本发明提及的所有文献都在本申请中引用作为参考，就如同每一篇文献被单独引用作为参考那样。此外应理解，在阅读了本发明的上述讲授内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。

Claims (15)

  1. 一种如通式I所示的荧光化合物，或其盐、对映异构体、非对映异构体、互变异构体、溶剂化物或多晶型物，其特征在于，具有结构
    Figure PCTCN2020073720-appb-100001
    其中，m、n各自独立地为0-10的整数；
    Y 1、Y 2各自独立地选自下组：氢、苯基、羟基、羧基、酯基、硼酸基、硼酸酯基、一个或多个硼酸基或硼酸酯基取代的3-7元环，且Y 1和Y 2至少一个为含硼的基团。
  2. 如权利要求1所述的荧光化合物，或其盐、对映异构体、非对映异构体、互变异构体、溶剂化物或多晶型物，其特征在于，Y 1、Y 2各自独立地选自下组：氢、苯基、硼酸基、硼酸酯基、
    Figure PCTCN2020073720-appb-100002
    且Y 1和Y 2不同时为氢，且Y 1和Y 2不同时为苯基；式中R 1、R 2各自独立地为羟基，或与它们连接的硼原子一起代表可水解为硼酸的基团。
  3. 如权利要求1所述的荧光化合物，或其盐、对映异构体、非对映异构体、互变异构体、溶剂化物或多晶型物，其特征在于，其盐具有式II结构
    Figure PCTCN2020073720-appb-100003
    其中，M表示与式II中的N形成盐的阴离子。
  4. 如权利要求3所述的荧光化合物，或其盐、对映异构体、非对映异构体、互变异构体、溶剂化物或多晶型物，其特征在于，M包括碘离子、氯离子、溴离子、烷基磺酸根、四氟硼酸根、硫酸根、硝酸根、磷酸根、或高氯酸根、甲酸根、乙酸根、苯丙氨酸根。
  5. 如权利要求1-3任一所述的荧光化合物，或其盐、对映异构体、非对映异构体、互变异构体、溶剂化物或多晶型物，其特征在于，m、n各自独立地为0-5的整数。
  6. 如权利要求1-3所述的荧光化合物，或其盐、对映异构体、非对映异构体、互变异构体、溶剂化物或多晶型物，其特征在于，具有结构
    Figure PCTCN2020073720-appb-100004
  7. 如权利要求1-3所述的荧光化合物，或其盐、对映异构体、非对映异构体、互变异构体、溶剂化物或多晶型物，其特征在于，B为 10B。
  8. 一种制备如权利要求1-3任一所述的荧光化合物或其盐的方法，其特征在于，所述方法包括使用式c化合物的步骤，所述式c化合物具有结构
    Figure PCTCN2020073720-appb-100005
    其中，m为0-10的整数；
    Y 1选自下组：氢、苯基、羟基、羧基、酯基、硼酸基、硼酸酯基、一个或多个硼酸基或硼酸酯基取代的3-7元环；
    优选地，式c化合物结构为
    Figure PCTCN2020073720-appb-100006
  9. 如权利要求8所述的方法，其特征在于，所述方法还包括步骤：(i)式a化合物与式b化合物反应，得到式c化合物
    Figure PCTCN2020073720-appb-100007
    其中，X为卤素；m为0-10的整数；
    Y 1选自下组：氢、苯基、羟基、羧基、酯基、硼酸基、硼酸酯基、一个或多个硼酸基或硼酸酯基取代的3-7元环。
  10. 如权利要求8所述的方法，其特征在于，所述方法还包括步骤：(ii)式c化合物、式c-1化合物与式d化合物反应，得到式I化合物
    Figure PCTCN2020073720-appb-100008
    式c化合物与式d化合物反应，得到式I化合物
    Figure PCTCN2020073720-appb-100009
    其中，m、n各自独立地为0-10的整数；
    Y 1、Y 2各自独立地选自下组：氢、苯基、羟基、羧基、酯基、硼酸基、硼酸酯基、一个或多个硼酸基或硼酸酯基取代的3-7元环；且Y 1和Y 2至少一个为含硼的基团。
  11. 如权利要求10所述的方法，其特征在于，所述式c-1化合物与式c化合物的合成方法相同。
  12. 如权利要求10所述的方法，其特征在于，所述式c-1化合物与式c化合物相同。
  13. 如权利要求8-10所述的方法，其特征在于，m为0-5的正整数；Y 1为
    Figure PCTCN2020073720-appb-100010
    式中R 1、R 2各自独立地为羟基，或与它们连接的硼原子一起代表可水解为硼酸的基团。
  14. 如权利要求8-10所述的方法，其特征在于，B为 10B。
  15. 一种如权利要求1-3任一所述荧光化合物，或其盐、对映异构体、非对映异构体、互变异构体、溶剂化物或多晶型物作为荧光染料的用途。
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