CN113416203A - Near-infrared-emitting thiadiazole quinoxaline fluorescent molecule with large Stokes shift and preparation method thereof - Google Patents
Near-infrared-emitting thiadiazole quinoxaline fluorescent molecule with large Stokes shift and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a near-infrared emitting thiadiazole quinoxaline fluorescent molecule with large Stokes shift and a preparation method thereof. The invention has the advantages that: a thiadiazole quinoxaline fluorescent molecule with the maximum fluorescence emission wavelength of more than 724nm and the Stokes shift of more than 138nm is designed and synthesized by the strategy of intramolecular proton hydrogen transfer and the formation of intramolecular electron push-pull system. The preparation method of the molecule comprises the steps of carrying out Suzuiki reaction on 4, 9-dibromo-thiadiazole quinoxaline and 2-benzothiazolyl-4-borate-phenol with intramolecular proton hydrogen transfer characteristic to obtain 4-bromo-9- (2-benzothiazolyl-phenol) thiadiazole quinoxaline, and carrying out Suzuki reaction on the 4-bromo-9- (2-benzothiazolyl-phenol) thiadiazole quinoxaline and aryl borate with electron-pushing performance to obtain the near infrared emission thiadiazole quinoxaline fluorescent molecule. The material can be applied to the fields of biological fluorescent probes, biological fluorescent imaging and the like.
Description
Technical Field
The invention belongs to the field of synthesis of fluorescent small molecular materials, and relates to a large-Stokes-shift near-infrared emission thiadiazole quinoxaline compound and a preparation method thereof.
Background
The fluorescence imaging technology based on the organic dye has the advantages of simple and convenient operation, good reproducibility and the like, and can realize in-situ and real-time nondestructive detection of biomolecules and tracking of biological processes. Among them, the near-infrared fluorescent dye with the fluorescence emission wavelength of more than 650nm has the advantages of small interference of biological background, low damage to cells, large light penetration depth and the like, has extremely wide application prospect in the aspects of tissue imaging and living body imaging, and has become a hot topic of fluorescent dye research in recent years. The Stokes shift is an important physical constant of the fluorescent dye, the fluorescent dye with large Stokes shift can well separate an excitation spectrum from an emission spectrum, complete emission spectrum data can be obtained under the action of the maximum excitation wavelength, and the interference of self-quenching can be reduced to the maximum extent, so that the signal-to-noise ratio of biological imaging is improved, and the sensitivity and the definition of fluorescent imaging are increased.
However, the stokes shift of conventional dyes (such as fluorescein, rhodamine, oxazine and cyanine) is small (typically <30nm), and the overlap between the excitation and emission spectra is severe, resulting in low signal-to-noise ratio for imaging. Based on the above, some methods for improving the Stokes shift of the dye are reported in the literature, and a patent CN104710815A discloses a novel rhodamine fluorescent dye with large Stokes shift and near-infrared fluorescence emission and a synthetic method thereof; patent CN104710817A discloses a coumarin near-infrared fluorescent dye with small molecular weight and large Stokes shift and a synthetic method thereof; patent CN107383067B discloses a method for preparing a near-infrared emitting xanthene fluorescent dye with large stokes shift, which achieves the purpose of red shift of fluorescence emission by expanding the conjugate plane of the dye, but has the disadvantages of multiple synthesis steps, low total yield and limited improvement of stokes shift.
In response to this problem, the present invention provides a new strategy to synthesize near-infrared emitting fluorescent dyes with large stokes shift. The excited state proton transfer process (ESIPT) has important function in the chemical and biological process of light induction, when light is excited, the enol form of the excited state can be quickly converted into the keto tautomer of the excited state, the process generates an emission band with large Stokes displacement, and the ESIPT molecule has the advantages of luminous intensity, large Stokes displacement, good light stability and the like. The thiadiazole quinoxaline is a conjugated structure with electron deficiency, an electron push-pull system is easily formed with an electron donor unit, so that the fluorescence emission is red-shifted, and the fluorescence spectrum of the electron donor unit can be conveniently regulated and controlled by changing the structure of the electron donor unit. At present, no document or patent reports the near-infrared emission thiadiazole quinoxaline compound with large Stokes shift and the preparation method thereof.
Disclosure of Invention
The invention aims to provide a near-infrared emitting thiadiazole quinoxaline compound with large Stokes shift and a preparation method thereof, aiming at the defects of small Stokes shift and long synthesis steps of the existing near-infrared fluorescent dye.
The purpose of the invention is realized by the following technical scheme.
A large Stokes shift near infrared emission thiadiazole quinoxaline compound has a chemical structural formula as follows:
the preparation method of the near-infrared emitting thiadiazole quinoxaline compound with large Stokes shift comprises the following steps:
(1) under the protection of inert gas, dissolving 4, 9-dibromo-thiadiazole quinoxaline and 2-benzothiazolyl-4-borate ester-phenol in a tetrahydrofuran-water mixed solvent, introducing the inert gas for 10-20 minutes, adding a palladium catalyst with a catalytic amount of 1-15 mol% of that of the 4, 9-dibromo-thiadiazole quinoxaline and 0.1-5 mol/L of alkaline aqueous solution, continuously introducing the inert gas for 10-20 minutes, heating to 50-80 ℃, stirring and refluxing for 6-24 hours, cooling to room temperature, sequentially washing with water, and performing CH (methyl) washing2Cl2Extracted anhydrous NaSO4Drying and carrying out column chromatography to obtain the 4-bromo-9- (2-benzothiazolyl-phenol) thiadiazole quinoxaline.
(2) Under the protection of inert gas, the product of the step (1) and the catalyst with the function of pushing electricityDissolving arylboronic acid ester with the sub-performance in a tetrahydrofuran-water mixed solvent, introducing inert gas for 10-20 minutes, adding a palladium catalyst with the catalyst amount of 1-10 mol% based on arylboronic acid ester and 0.1-10 mol/L of alkaline aqueous solution, continuously introducing inert gas for 10-20 minutes, heating to 50-80 ℃, stirring and refluxing for 6-36 hours, cooling to room temperature, washing with water, extracting with tetrahydrofuran and then introducing anhydrous NaSO4Drying and carrying out column chromatography to obtain the near-infrared emission thiadiazole quinoxaline fluorescent molecule.
Preferably, the arylborate in step (2) is a thienyl group-containing compound.
Preferably, the palladium catalyst in the step (1) and the step (2) is Pd (Pph)3)4、Pd(Pph3)2Cl2Or Pd (dppf) Cl2。
Preferably, the alkaline aqueous solution of step (1) and step (2) comprises Na2CO3Aqueous solution, Cs2CO3Aqueous solution, K2CO3Aqueous solution, aqueous KOH solution, or aqueous NaOH solution.
The principle of the invention is as follows: 4, 9-dibromo-thiadiazole quinoxaline and 2-benzothiazolyl-4-borate ester-phenol are subjected to a Suzuki reaction to obtain 4-bromo-9- (2-benzothiazolyl-phenol) thiadiazole quinoxaline, and further subjected to a Suzuki reaction with aryl borate ester with electron-pushing performance to obtain the near-infrared emission thiadiazole quinoxaline fluorescent molecule. The reaction formula is as follows:
compared with the prior art, the invention has the following advantages and technical effects:
(1) the thiadiazole quinoxaline nucleus with electron-withdrawing ability and the aryl with electron-donating ability form an electron push-pull system, so that the fluorescence emission of the final product is red-shifted.
(2) The ESIPT component (2-benzothiazolyl-phenol) gives the final product a large Stokes shift.
(2) The final product has both large Stokes shift and near infrared emission through the synergistic effect of intramolecular charge transfer and excited intramolecular proton transfer.
(4) Aryl groups with different electron donating effects can be introduced to conveniently adjust the fluorescence emission range and Stokes shift of products.
Drawings
FIG. 1 is a UV and fluorescence spectrum of TQ1 normalized in acetone prepared in example 1.
FIG. 2 is a UV and fluorescence spectrum of TQ1 normalized in toluene prepared in example 1.
FIG. 3 is a UV and fluorescence spectrum of TQ1 normalized in chloroform as prepared in example 1.
Detailed Description
The following examples are presented to further illustrate the practice of the invention, but the scope of the invention as claimed should not be limited to the examples.
Example 1
A large Stokes shift near infrared emitting thiadiazolo quinoxaline compound TQ1 was prepared.
(1)4, 9-dibromo-6, 7-bis (4-ethylphenyl) - [1, 2, 5] thiazole [3, 4-g ] quinoxaline was prepared according to the methods disclosed in documents h.li, t.l.tam, y.m.lam, s.g.mhaiskar, a.c.grimsdale, org.lett.2011,13,46 and 2-benzothiazolyl-4-boronate-phenol was prepared according to the documents. F Wu, L Wang, T Hao, C Cao, anal. chem.2019,91,5261.
(2) 10mmol of 4, 9-dibromo-6, 7-bis (4-ethylphenyl) - [1, 2, 5]]Thiazole [3, 4-g]Quinoxaline and 10mmol of 2-benzothiazolyl-4-borate-based-phenol were dissolved in 100mL of a tetrahydrofuran-water (1:1, v: v) mixed solvent, an inert gas was introduced for 20 minutes, and 15 mol% of a catalyst amount of Pd (Pph) based on 4, 9-dibromo-thiadiazole-quinoxaline was added3)4And 0.1mol/L sodium carbonate aqueous solution, continuously introducing inert gas for 10 minutes, heating to 65 ℃, stirring and refluxing for 18 hours, cooling to room temperature, washing with water, and sequentially introducing CH2Cl2Extracted anhydrous NaSO4Drying and column chromatography to obtain 4-bromo-9- (2-benzothiazolyl-phenol) -6, 7-bis (4-ethylphenyl) - [1, 2, 5]]Thiazole [3, 4-g]Quinoxaline as a red-black solid in yield45 percent;
(3) 10mmol of 4-bromo-9- (2-benzothiazolyl-phenol) -6, 7-bis (4-ethylphenyl) - [1, 2, 5]]Thiazole [3, 4-g]Quinoxaline and 10mmol of 2-thiopheneboronic acid pinacol ester are dissolved in 100mL of tetrahydrofuran-water (1:1, v: v) mixed solvent, inert gas is introduced for 20 minutes, and 10mol percent of catalytic amount of Pd (Pph) calculated by 2-thiopheneboronic acid pinacol ester is added3)4And 0.1mol/L sodium carbonate aqueous solution, continuously introducing inert gas for 10-20 minutes, heating to 55 ℃, stirring and refluxing for 24 hours, cooling to room temperature, washing with water, and sequentially introducing CH2Cl2Extracted anhydrous NaSO4Drying, and performing column chromatography (the volume ratio of petroleum ether, ethyl acetate and ethanol is 20:2:1) to obtain 4-thiophene-9- (2-benzothiazolyl-phenol) -6, 7-bis (4-ethylphenyl) - [1, 2, 5]]Thiazole [3, 4-g]Quinoxaline, as a violet black solid, in 50% yield.
TQ1 normalized ultraviolet and fluorescence spectra in toluene with ultraviolet and emission peaks at 588 and 726nm, respectively, and a Stokes shift of 138nm, as shown in FIG. 1.
TQ1 normalized ultraviolet and fluorescence spectra in acetone with ultraviolet and emission peaks at 568 and 726nm, respectively, and Stokes shift of 158nm, as shown in FIG. 2.
TQ1 normalized ultraviolet and fluorescence spectra in chloroform with ultraviolet and emission peaks at 570 and 724nm, respectively, and a Stokes shift of 144nm, as shown in FIG. 3.
Example 2
Preparation of large Stokes shift near infrared emitting thiadiazole quinoxaline compounds TQ 2.
(1)4, 9-dibromo-6, 7-bis (4-n-octadecylphenyl) - [1, 2, 5] thiazole [3, 4-g ] quinoxaline was prepared according to the methods disclosed in documents h.li, t.l.tam, y.m.lam, s.g.mhaiskar, a.c.grimsdale, org.lett.2011,13,46, and 2-benzothiazolyl-4-boronate-phenol was prepared according to the documents. F Wu, L Wang, T Hao, C Cao, anal. chem.2019,91,5261.
(2) 10mmol of 4, 9-dibromo-6, 7-bis (4-n-octadecyl phenyl) - [1, 2, 5]]Thiazole [3, 4-g]Quinoxaline and 10mmol of 2-benzothiazolyl-4-borate-phenol were dissolved in 100mL of tetrahydrofuranIn a mixed solvent of pyran-water (1:1, v: v), an inert gas was introduced for 20 minutes, and 15 mol% of a catalyst amount of Pd (Pph) based on 4, 9-dibromo-thiadiazoloquinoxaline (mole%)3)2Cl2And 0.1mol/L potassium carbonate aqueous solution, continuously introducing inert gas for 10-20 minutes, heating to 65 ℃, stirring and refluxing for 24 hours, cooling to room temperature, washing with water, and sequentially introducing CH2Cl2Extracted anhydrous NaSO4Drying and column chromatography to obtain 4-bromo-9- (2-benzothiazolyl-phenol) -6, 7-bis (4-n-octadecyl phenyl) - [1, 2, 5]]Thiazole [3, 4-g]Quinoxaline, as a red-black solid, in a yield of 45%;
(3) 10mmol of 4-bromo-9- (2-benzothiazolyl-phenol) -6, 7-bis (4-n-octadecyl phenyl) - [1, 2, 5]]Thiazole [3, 4-g]Quinoxaline and 10mmol of 2-furanboronic acid pinacol ester are dissolved in 100mL of tetrahydrofuran-water (1:1, v: v) mixed solvent, inert gas is introduced for 15 minutes, and 10 mol% of catalytic amount of Pd (Pph) calculated by 2-furanboronic acid pinacol ester is added3)2Cl2And 0.1mol/L potassium carbonate aqueous solution, continuously introducing inert gas for 15 minutes, heating to 50 ℃, stirring and refluxing for 24 hours, cooling to room temperature, washing with water, and sequentially introducing CH2Cl2Extracted anhydrous NaSO4Drying, and performing column chromatography (the volume ratio of petroleum ether, ethyl acetate and ethanol is 20:2:2) to obtain 4-furyl-9- (2-benzothiazolyl-phenol) -6, 7-bis (4-n-octadecyl phenyl) - [1, 2, 5]]Thiazole [3, 4-g]Quinoxaline, as a violet black solid, in 59% yield.
Example 3
Preparation of large Stokes shift near infrared emitting thiadiazole quinoxaline compounds TQ 3.
(1)4, 9-dibromo-6, 7-bis (4-alkoxymethylphenyl) - [1, 2, 5] thiazole [3, 4-g ] quinoxaline was prepared according to the methods disclosed in documents h.li, t.l.tam, y.m.lam, s.g.mhaiskar, a.c.grimsdale, org.lett.2011,13,46, and 2-benzothiazolyl-4-boronate-phenol was prepared according to the documents. F Wu, L Wang, T Hao, C Cao, anal. chem.2019,91,5261.
(2) 10mmol of 4, 9-dibromo-6, 7-bis (4-alkoxymethylphenyl) - [1, 2, 5]]Thiazole [3, 4-g]Quinoxaline and 10mmol of 2-benzothiazolyl-4-borate-phenolDissolved in 100mL of tetrahydrofuran-water (1:1, v: v) mixed solvent, passed through inert gas for 20 minutes, and added with 15 mol% of catalyst amount of Pd (Pph) calculated by 4, 9-dibromo-thiadiazole quinoxaline3)4And 0.1mol/L cesium carbonate aqueous solution, continuously introducing inert gas for 10-20 minutes, heating to 60 ℃, stirring and refluxing for 12 hours, cooling to room temperature, washing with water, and sequentially introducing CH2Cl2Extracted anhydrous NaSO4Drying and column chromatography to obtain 4-bromo-9- (2-benzothiazolyl-phenol) -6, 7-bis (4-alkoxymethylphenyl) - [1, 2, 5]]Thiazole [3, 4-g]Quinoxaline, as a red-black solid, in a yield of 40%;
(3) 10mmol of 4-bromo-9- (2-benzothiazolyl-phenol) -6, 7-bis (4-alkoxymethylphenyl) - [1, 2, 5]]Thiazole [3, 4-g]Quinoxaline and 10mmol of 2-phenylboronic acid pinacol ester are dissolved in 100mL of tetrahydrofuran-water (1:1, v: v) mixed solvent, inert gas is introduced for 20 minutes, and 10 mol% of catalytic amount of Pd (Pph) calculated by 2-phenylboronic acid pinacol ester is added3)4And 0.5mol/L sodium carbonate aqueous solution, continuously introducing inert gas for 10-20 minutes, heating to 55 ℃, stirring and refluxing for 24 hours, cooling to room temperature, washing with water, and sequentially introducing CH2Cl2Extracted anhydrous NaSO4Drying, and performing column chromatography (the volume ratio of petroleum ether, ethyl acetate and ethanol is 20:2:0.5) to obtain 4-phenyl-9- (2-benzothiazolyl-phenol) -6, 7-bis (4-alkoxymethylphenyl) - [1, 2, 5]]Thiazole [3, 4-g]Quinoxaline, as a violet black solid, in 43% yield.
Example 4
Preparation of large Stokes shift near infrared emitting thiadiazole quinoxaline compounds TQ 4.
(1)4, 9-dibromo-6, 7-bis (4-isooctylphenyl) - [1, 2, 5] thiazole [3, 4-g ] quinoxaline was prepared according to the methods disclosed in documents h.li, t.l.tam, y.m.lam, s.g.mhaiskar, a.c.grimsdale, org.lett.2011,13,46, and 2-benzothiazolyl-4-boronate-phenol was prepared according to the documents. F Wu, L Wang, T Hao, C Cao, anal. chem.2019,91,5261.
(2) 10mmol of 4, 9-dibromo-6, 7-bis (4-isooctylphenyl) - [1, 2, 5]]Thiazole [3, 4-g]Quinoxaline and 10mmol of 2-benzothiazolyl-4-borate-phenol were dissolved in 100mL of tetrahydrofuranIn a mixed solvent of pyran-water (1:1, v: v), an inert gas was introduced for 20 minutes, and 15 mol% of a catalyst amount of Pd (Pph) based on 4, 9-dibromo-thiadiazoloquinoxaline (mole%)3)4And 0.1mol/L cesium carbonate aqueous solution, continuously introducing inert gas for 10-20 minutes, heating to 60 ℃, stirring and refluxing for 24 hours, cooling to room temperature, washing with water, and sequentially introducing CH2Cl2Extracted anhydrous NaSO4Drying and column chromatography to obtain 4-bromo-9- (2-benzothiazolyl-phenol) -6, 7-bis (4-isooctylphenyl) - [1, 2, 5]]Thiazole [3, 4-g]Quinoxaline, as a red-black solid, in a yield of 48%;
(3) 10mmol of 4-bromo-9- (2-benzothiazolyl-phenol) -6, 7-bis (4-isooctylphenyl) - [1, 2, 5]]Thiazole [3, 4-g]Quinoxaline and 10mmol of (4-methoxy) pinacol ester of phenylboronic acid are dissolved in 100mL of tetrahydrofuran-water (1:1, v: v) mixed solvent, inert gas is introduced for 20 minutes, and 10 mol% of catalytic amount of Pd (Pph) calculated by 4-methoxy) pinacol ester of phenylboronic acid is added3)4And 0.1mol/L sodium carbonate aqueous solution, continuously introducing inert gas for 10-20 minutes, heating to 55 ℃, stirring and refluxing for 36 hours, cooling to room temperature, washing with water, and sequentially introducing CH2Cl2Extracted anhydrous NaSO4Drying, and performing column chromatography (the volume ratio of petroleum ether, ethyl acetate and ethanol is 20:1:0.5) to obtain 4- (4-methoxyphenyl) phenyl-9- (2-benzothiazolyl-phenol) -6, 7-bis (4-isooctylphenyl) - [1, 2, 5]]Thiazole [3, 4-g]Quinoxaline, as a violet black solid, in 43% yield.
Example 5
Preparation of large Stokes shift near infrared emitting thiadiazole quinoxaline compounds TQ 5.
(1)4, 9-dibromo-6, 7-bis (4-isooctylphenyl) - [1, 2, 5] thiazole [3, 4-g ] quinoxaline was prepared according to the methods disclosed in documents h.li, t.l.tam, y.m.lam, s.g.mhaiskar, a.c.grimsdale, org.lett.2011,13,46, and 2-benzothiazolyl-4-boronate-phenol was prepared according to the documents. F Wu, L Wang, T Hao, C Cao, anal. chem.2019,91,5261.
(2) 10mmol of 4, 9-dibromo-6, 7-bis (4-isooctylphenyl) - [1, 2, 5]]Thiazole [3, 4-g]Quinoxaline and 10mmol of 2-benzothiazolyl-4-borate-phenol are dissolved in 100mL of tetrahydrofuran-water (1:1, v: v) mixed solvent, introducing inert gas for 20 minutes, and adding 15 mol% of Pd (Pph) in terms of 4, 9-dibromo-thiadiazole quinoxaline based catalyst amount3)4And 0.1mol/L cesium carbonate aqueous solution, continuously introducing inert gas for 10-20 minutes, heating to 60 ℃, stirring and refluxing for 24 hours, cooling to room temperature, washing with water, and sequentially introducing CH2Cl2Extracted anhydrous NaSO4Drying and column chromatography to obtain 4-bromo-9- (2-benzothiazolyl-phenol) -6, 7-bis (4-isooctylphenyl) - [1, 2, 5]]Thiazole [3, 4-g]Quinoxaline, as a red-black solid, in a yield of 42%;
(3) 10mmol of 4-bromo-9- (2-benzothiazolyl-phenol) -6, 7-bis (4-isooctylphenyl) - [1, 2, 5]]Thiazole [3, 4-g]Quinoxaline and 10mmol (5-thienyl) -2-thiopheneboronic acid pinacol ester are dissolved in 100mL tetrahydrofuran-water (1:1, v: v) mixed solvent, inert gas is introduced for 20 minutes, and 10 mol% of catalytic amount of Pd (Pph mol%) based on 5-thienyl) -2-thiopheneboronic acid pinacol ester is added3)4And 0.1mol/L sodium carbonate aqueous solution, continuously introducing inert gas for 10-20 minutes, heating to 50 ℃, stirring and refluxing for 24 hours, cooling to room temperature, washing with water, and sequentially introducing CH2Cl2Extracted anhydrous NaSO4Drying, and performing column chromatography (the volume ratio of petroleum ether, ethyl acetate and ethanol is 15:2:0.5) to obtain 4- (5-thienyl thiophene) -9- (2-benzothiazolyl-phenol) -6, 7-bis (4-isooctylphenyl) - [1, 2, 5]]Thiazole [3, 4-g]Quinoxaline, as a violet black solid, in 42% yield.
Claims (8)
1. A near-infrared emitting thiadiazole quinoxaline fluorescent molecule with large Stokes shift is characterized in that the chemical structural formula is as follows:
2. the near infrared emitting thiadiazoloquinoxaline fluorescent molecule having a large stokes shift according to claim 1, wherein:
3. the method for preparing the near-infrared-emitting thiadiazole-quinoxaline fluorescent molecule with large stokes shift according to claim 1, which is characterized by comprising the following steps:
4. the method for preparing a near-infrared-emitting thiadiazoloquinoxaline fluorescent molecule having a large stokes shift according to claim 3, comprising the steps of:
(1) under the protection of inert gas, dissolving 4, 9-dibromo-thiadiazole quinoxaline and 2-benzothiazolyl-4-borate ester-phenol in a tetrahydrofuran-water mixed solvent, introducing the inert gas for 10-20 minutes, adding a palladium catalyst with a catalytic amount of 1-15 mol% of that of the 4, 9-dibromo-thiadiazole quinoxaline and 0.1-5 mol/L of alkaline aqueous solution, continuously introducing the inert gas for 10-20 minutes, heating to 50-80 ℃, stirring and refluxing for 6-24 hours, cooling to room temperature, sequentially washing with water, and performing CH (methyl) washing2Cl2Extracted anhydrous NaSO4Drying and carrying out column chromatography to obtain the 4-bromo-9- (2-benzothiazolyl-phenol) thiadiazole quinoxaline.
(2) Under the protection of inert gas, dissolving the product obtained in the step (1) and arylboronic acid ester with electron-pushing performance in a tetrahydrofuran-water mixed solvent, introducing the inert gas for 10-20 minutes, adding a palladium catalyst with the amount of 1-10 mol% of the arylboronic acid ester and 0.1-10 mol/L of an alkaline aqueous solution, continuously introducing the inert gas for 10-20 minutes, heating to 50-80 ℃, stirring and refluxing for 6-36 hours, cooling to room temperature, sequentially washing with water, extracting with tetrahydrofuran, and extracting with anhydrous NaSO4Drying and carrying out column chromatography to obtain the near-infrared emission thiadiazole quinoxaline fluorescent molecule.
5. The method of claim 4 for preparing a near infrared emitting thiadiazole quinoxaline fluorescent molecule having a large stokes shift, which comprises: an eluant petroleum ether, ethyl acetate and ethanol mixture used in the step (2) column chromatography, wherein the volume ratio of the eluant petroleum ether, the ethyl acetate and the ethanol mixture is 15-20: 0.5-2: 0.8-1.5.
6. The process according to claim 4, wherein the arylboronic acid ester having an electron-donating property in the step (2) is a benzene ring compound having an electron-donating group or an aromatic compound containing a sulfur atom or an oxygen atom.
7. The method according to claim 4, wherein the palladium catalyst in the step (1) and the step (2) is Pd (Pph)3)4、Pd(Pph3)2Cl2Or Pd (dppf) Cl2。
8. The method according to claim 4, wherein the alkaline aqueous solution of step (1) and step (2) comprises Na2CO3Aqueous solution, Cs2CO3Aqueous solution, K2CO3Aqueous solution, aqueous KOH solution, or aqueous NaOH solution.
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