CN107057397A - Perylene tetracarboxylic acid fluorine boron pyrroles's binary dye and preparation method thereof - Google Patents
Perylene tetracarboxylic acid fluorine boron pyrroles's binary dye and preparation method thereof Download PDFInfo
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- C09B5/00—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings
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Abstract
Gong Kai perylene tetracarboxylic acids fluorine boron pyrroles's binary dye of the present invention and preparation method thereof, the binary dye has following general structure I and formula II：R in formula1And R2For alkyl, R3For alkoxy or hydrogen-based.The invention discloses three kinds of new compounds, the scope of compound is expanded, is that noval chemical compound performance study provides the foundation.
Description
Technical field
The invention belongs to organic dyestuff field used in electro transfer, organic solar batteries field, and in particular to Yi Zhong perylenes
Tetrabasic carboxylic acid-fluorine boron pyrroles's binary dye and preparation method thereof.
Background technology
In face of current energy shortage, many environmental problems that fossil energy consumption is brought, solar cell and light promote electronics
The research of transfer is increasingly paid close attention to by people.In organic functional material, there is D-A type organic dyestuff broad spectrum to inhale
Scope is received, the focus of research can be turned into the level structure of accuracy controlling.Perylene tetracarboxylic acid ester is famous N-type semiconductor material,
With the hope for realizing photoelectric transformation efficiency new breakthrough；BODIPY has remarkable chemistry, physical property, can be by organic
Synthesis is easily able to prepare and modified, and is widely used in biological field and energy field.
Light promotees the Gibbs free energy of electro transfer, can according to formula 1, by the oxidation-reduction potential of binary material,
First excited state energy level, coulomb are acted on calculating, and electron transfer rate constant can be calculated according to Marcus equations.
The content of the invention
In view of this, the purpose of the present invention is that BODIPY derived from vinyl is passed through into conjugation Lian Jie Dao perylene tetracarboxylic acid
On derivative, by the electron-withdrawing power of Bian Huan perylene tetracarboxylic acid derivatives, regulate and control spectrum, the energy level performance of binary dye, for up to
To above-mentioned purpose, the present invention uses following technical scheme：
Perylene tetracarboxylic acid-fluorine boron pyrroles's binary dye, the binary dye has following general structure I and formula II：
R in formula1And R2For alkyl, R3For alkoxy or hydrogen-based.
Further, the R1For amyl group, R2For butyl, R3For methoxyl group or hydrogen-based.
The preparation method of the binary dye, is comprised the following steps：
(1) synthesis of the bromo- 7 Jia Yang Ji perylene tetracarboxylic acids esters of 1- Xiu perylene tetracarboxylic acids ester/1- and its derivative, its reaction equation is such as
Under：
(1-1) perylene tetracarboxylic acids esters and 1.0-20eq bromines, in the presence of 0.1eq-100eq alkali, reaction in a solvent is obtained
Single Xiuization perylene tetracarboxylic acid ester；
(1-2) 1,7 2 bromine perylene tetracarboxylic acid ester and alcohol are in 0.01eq-100eq metals copper catalyst, 0.1eq-100eq alkali
Under the conditions of react in a solvent, obtain the bromo- 7 Wan Yang Ji perylene tetracarboxylic acid esters of 1-；
(2) synthesis of BODIPY borates：Bromination substrate B ODIPY reacts through suzuki miyaura, obtains BODIPY boric acid
Ester, reaction condition is in the presence of palladium catalyst, metallic catalyst, double (pinacol conjunctions) two boron and alkali is placed in solvent, control
Reaction temperature reacts 1-100h at 30-200 DEG C；Reaction equation is as follows：
(the preparation of 3) perylene tetracarboxylic acids-fluorine boron pyrroles's binary dye：
(3-1) is by step 1-1), 2) gained compound is coupled through Suzuki, He Cheng Chu perylene tetracarboxylic acids-pyrroles of fluorine boron two spreads out
Biology, its specific reaction condition is Xiuization perylene tetracarboxylic acid ester, metallic catalyst, BODIPY borates, alkali, is added in solvent,
Controlling reaction temperature reacts 1-100h at 30-200 DEG C, purified to obtain target product；Reaction equation is as follows：
(3-2) is by step 1-2), 2) gained compound is coupled through Suzuki, He Cheng Chu perylene tetracarboxylic acids-fluorine boron pyrroles's binary
Dyestuff, its specific reaction condition is Dan Xiu perylene diimides, metallic catalyst, BODIPY borates, alkali, is added in solvent, is controlled
Reaction temperature processed reacts 1-100h at 30-200 DEG C, purified to obtain target product；Reaction equation is as follows：
R in formula1For amyl group, R2For butyl, R3 is methoxyl group or hydrogen-based.
Further, step 1-1) the 1- Xiu perylene tetracarboxylic acid esters synthesis, the alkali be Na2CO3Or K2CO3；It is described
Solvent is tetrahydrofuran, dioxane, DMF or N, N dimethyl acetamide.
Further, step 1-2) described 1,7 Er Xiu perylene tetracarboxylic acid esters synthesis, the alkali be Na2CO3Or K2CO3, gold
It is CuI, CuBr or copper powder to belong to copper catalyst；The solvent is tetrahydrofuran, dioxane, DMF or N, N bis-
Methylacetamide.
Further, step 2) the BODIPY borates synthesis in, Au catalyst is tetra-triphenylphosphine palladium, and two is chloro-
The double Diphenyl phosphino ferrocene palladium chlorides of bis-triphenyl phosphine palladium, palladium or 1,1'-；Alkali is Na2CO3、K2CO3, NaOAc or
KOAc；Solvent is toluene, dioxane, tetrahydrofuran or dimethyl sulfoxide (DMSO)；Reaction temperature is 0-150 DEG C.
Further, step 3) reaction temperature be 0-150 DEG C；Reaction dissolvent be toluene, dioxane, DMSO,
THF；Alkali is potassium acetate, sodium acetate, Na2CO3、K2CO3；The catalyst is Pd (PPh3) 4、Pd(PPh3)2Cl2、PdCl2
(dppf)、PdCl2/PPh3Or palladium；The purification process is silica gel column chromatography, chromatographic solution volume ratio dichloromethane/petroleum ether
=1/20-5/1.
In order to synthesize target product of the present invention, we have synthesized a series of substrate first, and its synthetic method and sign are such as
Under：
Compound 1：The synthetic route of 8- (4- bromophenyls) -1,3,5,7- tetramethyls-pyrroles of fluorine boron two：
4- bromobenzoic acids (5.0g, 25mmol) and SOCl2(12.5ml) 80 DEG C of reaction 3h.After cooling, it is unnecessary to spin off
SOCl2.Then the CH that 50mL is dried is added2Cl2, and add the 20mL of 2,4- dimethyl pyrroles (4.6g, 48.4 mmol)
CH2Cl2Solution, then stirring at normal temperature 20h. additions 10mL triethylamines, BF is added after 15 minutes3·OEt2(10mL,
81.4mmol), and 2h is stirred.Reactant mixture adds water and CH2Cl2, separate organic phase, Na2SO4Dry and desolvation.
Column chromatography for separation obtains compound 1, red solid (2.4 g, 24.6%)1H NMR(400MHz,CDCl3) δ 7.64 (d, J=
7.9Hz, 2H), 7.18 (d, J=7.9Hz, 2H), 5.99 (s, 2H), 2.55 (s, 6H), 1.41 (s, 6H).
Compound 2：Brominated BODIPY synthesis
Compound 1 (670mg, 1.66mmol), 15mg p-TsOHH2O, 4- dimethylamine benzaldehyde (543mg,
3.64mmol), and 0.5g of 4A molecular sieves are added in 50ml reaction bulbs, and with after nitrogen displacement 3 times, add 30mL
Toluene and 0.75mL piperidines, back flow reaction 70h.Reactant mixture is washed with water p-methyl benzenesulfonic acid and removes solvent, by silica gel
Post separation (from dichloromethane/petroleum ether=3/7 to absolute dichloromethane elute) obtain green solid compound 2 (605mg,
24.6%).1H NMR(400MHz,CDCl3) δ 7.63 (d, J=8.1Hz, 2H), 7.54 (d, J=8.3Hz, 6H), 7.23 (d, J
=8.2Hz, 4H), 6.71 (d, J=8.3Hz, 4H), 6.60 (s, 2H), 3.03 (s, 12H), 1.46 (s, 6H)13C NMR
(100MHz,CDCl3) δ153.43,151.26,140.89,136.96,135.06,133.06,132.44,131.06,
129.44,125.45, 123.24,117.75,115.24,112.44,40.56,29.99,15.15.HRMS(EI),M/Z:
cacld for[M]+, 664.2184；found,664.2213.
The beneficial effects of the invention are as follows：
1. Ti Gong perylene tetracarboxylic acids of the present invention-fluorine boron pyrroles's binary dye, disclose three kinds of new compounds, chemical combination is expanded
The scope of thing, is that noval chemical compound performance study provides the foundation.
2. the preparation method , perylene tetracarboxylic acid esters of Hai Ti Gong perylene tetracarboxylic acids of the present invention-fluorine boron pyrroles's binary dye are famous
N-type semiconductor material, with the hope for realizing photoelectric transformation efficiency new breakthrough；BODIPY has the chemical, physical of brilliance
Matter, can be easily able to prepare and modify by organic synthesis, be widely used in biological field and energy field.The present invention will
The two is cleverly combined, and realizes the fusion of its function, new carrier is provided for the research of organic dyestuff.
It is compound in green 3. the present invention has carried out substantial amounts of experiment test and theoretical research to compound light performance
The application of energy field provides theoretical foundation.
Brief description of the drawings
Accompanying drawing 1 is the uv-visible absorption spectra of compound；
Accompanying drawing 2 is the energy level of frontier orbital figure of compound, and second is classified as DPV test datas, and first, which is classified as DFT, calculates number
According to.
Embodiment
Embodiment 1
Compound OMePTAC-BODIPY synthesis, comprises the following steps：
(1) synthesis of the bromo- 7- Wan Yang Ji perylene tetracarboxylic acid esters of 1-, its reaction equation is as follows：
Concrete operations, K2CO3(690mg, 5.0mmol), bromo- 3,4,9,10- tetra- (the n-butoxycarbonyl)-perylenes of 1,7- bis-
(810mg,1.0mmol),0.2mL CH380 DEG C of reaction 24h of OH and 30mL DMF.It is cooled to room temperature 30mL water and adds and is used in combination
100mL CH2Cl2Extraction, organic phase is washed with water 3 times and uses Na2SO4Dry, after solvent evaporated, cross silicagel column.Using
CH2Cl2-PE(v/v 1:1) pure CH is arrived2Cl2As eluent, compound 4 (292mg, 77.6%) is obtained, and it is thick to reclaim 410mg
Product.1H NMR(400MHz,CDCl3) δ 8.98 (d, J=7.9Hz, 1H), 8.93 (d, J=8.1Hz, 1H), 8.29 (s, 1H),
8.08 (d, J=8.1Hz, 1H), 7.99 (d, J=7.9Hz, 1H), 4.33 (m, 8H), 4.15 (s, 3H), 1.85-1.70 (m,
8H), 1.48 (d, J=6.9Hz, 8H), 0.98 (m, 12H)13C NMR(100MHz,CDCl3)δ168.69,168.54,
168.34,167.65,155.58,136.76,133.04,132.34,132.24,131.96,131.41,130.55,
130.27,130.14,128.92,128.06,127.29,127.05,123.10,118.63,117.94,117.88, 65.88,
65.85,65.66,65.54,56.91,30.97,30.91,30.88,29.97,19.56,19.53,14.05.
(2) synthesis of BODIPY borates：Reaction equation is as follows：
Under concrete operations, nitrogen atmosphere, compound 2 (400mg, 0.60mmol), Pd (PPh3)2Cl2(130mg,
0.18mmol), the boron of duplex pinacol base two (760mg, 3.0mmol), potassium acetate (588mg, 6mmol) and 40mL dry toluenes
It is added in 100mL there-necked flasks.After the reaction overnight that flows back, it is cooled to room temperature, adds 50ml water, filtering by diatomite has separated
Machine phase, aqueous phase is extracted with dichloromethane, and merges organic phase, and rotation desolventizing obtains the mixture of green solid after drying.Should
Mixture adds 120ml n-hexanes and evaporates n-hexane after embathing 1h, filtering, obtains compound 3 (421mg, 98.6%)1H
NMR(400MHz,CDCl3) δ 7.90 (d, J=7.5Hz, 2H), 7.55 (m, 6H), 7.35 (d, J=7.5Hz, 2H), 7.18 (m,
2H), (d, J=7.2Hz, the 18H) of 6.72 (d, J=8.5Hz, 4H), 6.59 (s, 2H), 3.03 (s, 12H), 1.4013C NMR
(100 MHz,CDCl3)δ153.17,151.18,141.28,138.91,136.59,135.41,133.07,129.36,
128.54,125.54,117.50,115.39,112.44,84.37,40.56,25.25,15.03.HRMS(EI),M/Z:
cacld for[M]+,712.3931；found,712.3941.
(3) perylene tetracarboxylic acids-fluorine boron pyrroles binary dye OMePTAC-BODIPY preparation, reaction equation is as follows：
Concrete operations：N2Under atmosphere, compound 4 (125.0mg, 0.165mmol), BODPIY boric acid ester compounds 3
(129mg,0.181mmol),Pd(PPh3)4(19.0mg,0.0164mmol),Na2CO3(53.2mg, 0.493mmol),10mL
Dry THF, 1mL water are added to 25ml reaction bulbs, and back flow reaction 24h. is cooled to room temperature, add 10mL water and use 60mL
CH2Cl2Extraction 3 times, Na2SO4Dry, evaporate solvent, cross silicagel column, use A dichloromethane/petroleum ether (v/v 1:1) pure two are arrived
Chloromethanes finally using the dichloromethane eluent containing 1% triethylamine, and is recrystallized with dichloromethane-ethanol, obtained as eluant, eluent
To OMePTAC-BODIPY (76.0mg, 36.5%), green powder solid1H NMR(400MHz, CDCl3)δ9.02(d,J
=7.9Hz, 1H), 8.17-8.07 (m, 2H), 7.93 (s, 1H), 7.72 (d, J=7.9 Hz, 1H), 7.57 (m, 8H), 7.41
(d, J=7.6Hz, 2H), 7.37 (d, J=7.4Hz, 1H), 7.21 (m, 2H), 6.73 (d, J=8.1Hz, 4H), 6.64 (s,
2H),4.46–4.24(m,8H),4.19(s,3H),3.04(s,12H), 1.83–1.73(m,8H),1.55–1.41(m,14H),
1.10–0.90(m,12H).13C NMR(100 MHz,CDCl3)δ168.88,168.68,168.41,155.80,144.34,
137.77,134.43,132.78, 132.45,132.38,132.01,131.87,130.71,130.56,130.36,
129.68,129.62,129.43, 129.04,127.59,127.14,126.98,123.56,119.58,118.35,
112.52,68.21,65.91,65.74, 65.52,57.04,40.51,31.04,31.00,30.91,19.58,19.55,
14.15,14.08.HRMS(EI), M/Z:cacld for[M]+,1266.6065；found,1266.6042.
Embodiment 2
Compound PTAC-BODIPY synthesis, comprises the following steps：
(1) 1- bromo- 3, the synthesis of 4,9,10- tetra- (n-butoxycarbonyl)-perylene, reaction equation is as follows：
Concrete operations：The perylenes (3.0g, 4.6mmol) of 3,4,9,10- tetra- (n-butoxycarbonyl)-, K2CO3(3.0g,
21.7mmol),50mL CH2Cl2With 3mL Br2Stirring at normal temperature 1.5h.Excessive bromine Na2SO3The aqueous solution is washed products off and passed through
Column chromatography purifies (CH2Cl2Elution).Obtain the bromo- perylene of 3,4,9,10- tetra- (n-butoxycarbonyl)-(0.85g, the 25.2%) of 1-1H
NMR(400MHz,CDCl3) δ 9.16 (d, J=8.0Hz, 1H), 8.32 (s, 1H), 8.25 (dd, J=8.0,2.4Hz, 2H),
8.15–8.05(m,3H), 4.39–4.26(m,8H),1.79(m,8H),1.49(m,8H),0.99(m,12H).
(2) synthesis of BODIPY borates：See the step 2 of embodiment 1)；
(3) perylene tetracarboxylic acids-fluorine boron pyrroles binary dye PTAC-BODIPY synthesis, reaction equation is as follows：
Concrete operations, N2Under atmosphere, compound 5 (73.0mg, 0.1mmol), BODPIY boric acid ester compounds 3 (81.9mg,
0.115mmol),Pd(PPh3)4(11.6mg,0.01mmol),Na2CO3(31.8mg, 0.3mmol), the THF that 5mL is dried,
0.5mL water is added to 25ml reaction bulbs, and back flow reaction 24h. is cooled to room temperature, adds 5mL water and uses 30mL CH2Cl2Extraction 3 times,
Na2SO4Dry, evaporate solvent, cross silicagel column, use A dichloromethane/petroleum ether (v/v 1:1) it is used as elution to absolute dichloromethane
Agent, finally using the dichloromethane eluent containing 1% triethylamine, and is recrystallized with dichloromethane-ethanol, obtains PTAC-BODIPY
(59.0mg, 47.7%), green powder solid.1H NMR(400MHz,CDCl3) δ 8.32 (d, J=5.5Hz, 2H), 8.12
(m, 3H), 7.80 (d, J=7.8Hz, 1H), 7.62 (d, J=7.8Hz, 3H), 7.56 (d, J=8.2Hz, 5H), 7.49-
7.42 (m, 3H), 7.22 (d, 2H), 6.73 (d, J=8.4Hz, 4H), 6.65 (s, 2H), 4.34 (m, 8.1Hz, 8H), 3.04
(s,12H),1.83–1.73(m,8H),1.50(m,14H),1.00(m,12H). 13C NMR(100MHz,CDCl3)δ168.56,
159.49,151.25,144.76,138.77,138.18, 136.86,136.14,135.68,135.02,133.42,
132.18,131.75,131.21,130.96, 130.58,130.30,130.11,129.90,129.44,129.24,
129.08,127.23,125.50,124.35, 122.68,120.99,117.74,117.31,115.35,113.39,
112.46,105.72,65.72,65.60, 40.56,33.48,30.96,22.16,19.55,17.90,14.07,
11.74.HRMS(EI),M/Z:cacld for[M]+,1236.5959；found,1236.5920.
Embodiment 3
Compound PBI-BODIPY synthesis, comprises the following steps,
(1) the bromo- N of 1-, N- bis--(synthesis of ethyl propyl) perylene diimides, reaction equation is as follows,
Concrete operations：N, N- bis--(ethyl propyl) perylene diimides (0.7g, 1.32mmol), Br2(3.4mL,
68.6mmol),K2CO3(0.7g, 5.1mmol), 15mL CHCl3It is added in 100mL reaction bulbs, back flow reaction 4h. organic phases
Use saturation Na2SO3Aqueous solution washing to remove excessive bromine, after concentration organic phase column chromatographies to target compound 6 (0.35g,
43.5%), red solid1HNMR (400MHz,CDCl3) δ 9.81 (d, J=8.2Hz, 1H), 8.93 (s, 1H), 8.70 (d, J
=8.2Hz, 3H), 8.63 (d, J=8.0Hz, 2H), 5.17-4.99 (m, 2H), 2.26 (m, 4H), 2.02-1.87 (m, 4H),
0.92(m,12H).
(2) synthesis of BODIPY borates：See the step 2 of embodiment 1)；
(3) perylene tetracarboxylic acids-fluorine boron pyrroles binary dye PBI-BODIPY synthesis, reaction equation is as follows,
Concrete operations：N2Under atmosphere, compound 6 (60.8mg, 0.1mmol), BODPIY boric acid ester compounds 3
(78.3mg,0.11mmol),Pd(PPh3)4(11.6mg,0.01mmol),Na2CO3(31.8mg, 0.3 mmol), what 5mL was dried
THF, 0.5mL water are added to 25ml reaction bulbs, and back flow reaction 24h. is cooled to room temperature, add 5mL water and use 30mL CH2Cl2Extraction 3
It is secondary, Na2SO4Dry, evaporate solvent, cross silicagel column, use A dichloromethane/petroleum ether (v/v 1:1) absolute dichloromethane conduct is arrived
Eluant, eluent, finally using the dichloromethane eluent containing 1% triethylamine, and is recrystallized with dichloromethane-ethanol, obtain PBI-
BODIPY (48.0mg, 43.1%), black solid.1H NMR(400MHz,CDCl3)δ8.69(m, 4H),8.59(s,1H),
8.14 (d, J=8.2Hz, 1H), 8.05 (d, J=8.1Hz, 1H), 7.68 (d, J=7.9 Hz, 2H), 7.56 (m, 8H), 7.21
(m,2H),6.69(m,6H),5.07(m,2H),3.04(s,12H),2.27 (m,4H),2.05–1.86(m,7H),1.52(s,
3H),1.02–0.84(m,12H).13C NMR(100MHz, CDCl3)δ151.27,144.00,141.15,137.07,
136.58,135.24,134.69,132.98,131.53, 130.51,129.56,129.48,129.04,127.90,
125.45,123.98,123.19,117.95,115.26, 112.44,100.29,58.16,58.04,40.56,25.39,
25.34,11.64.HRMS(EI),M/Z:cacld for [M]+,1114.5128；found,1114.5125.
The detection of compound spectra performance and light promote the theoretical calculation of electric charge transfer
1. the uv-visible absorption spectra of compound
Fig. 1 are the purple of three compound OMePTAC-BODIPY, PTAC-BODIPY, PBI-BODIPY and compound 2
Outside-visible absorbance collection of illustrative plates.Three compound OMePTAC-BODIPY, PTAC-BODIPY, PBI-BODIPY contaminate for exemplary binary
Expect structure, the absorption band of two kinds of modules of uv-visible absorption spectra Jian Ju perylene tetracarboxylic acids derivatives and BODIPY.Can from collection of illustrative plates
To find out, the maximum absorption wavelength of 4 compounds is all at 708nm；Compared with BODIPY compounds 2, the absorption of binary dye is bright
Aobvious enhancing, especially at 380-600nm.This enhancing can be tied in the absorption of perylene tetracarboxylic acid derivative with returning.Therefore, binary contaminates
The broad absorption of material, can there is more preferable match with solar spectrum.
2. the energy level of frontier orbital figure of compound, second is classified as DPV test datas, and first, which is classified as DFT, calculates data.
Fig. 2 is the HOMO/LUMO energy levels of binary dye, it can be seen that the energy level either calculated still tests what is measured
Energy level, all the HOMO energy levels with similar rule, i.e. material closely, the shadow of Ji this Bu Shou perylene tetracarboxylic acid deriveding groups
Ring, and the lumo energy of three kinds of materials differs greatly, and significantly reduced according to the enhancing of receptor unit electron-withdrawing power.Cause
This, Tong Guo combine perylene tetracarboxylic acid derivative with BODIPY, are capable of the energy level of frontier orbital of accurate controlled material.
The driving force of the Photoinduced charge transfer of 1. 3 kinds of binary dyes of table, separation of charge, compound free energy and speed
According to calculating, the electronics coupled of separation of charge and recombination process is 1.7 × 10 respectively-2EV and 2.2 × 10-2eV
(CS is Process of Charge Separation, and CR is charge recombination process).Due to Δ GCSIt is negative value, so the photic electricity of three kinds of binary dyes
Lotus separation state spontaneous can be produced.Compare separation of charge speed and charge recombination speed Ke to find out that , perylene tetracarboxylic acids ester derives
Binary dye, separation of charge speed is almost 1000 times of charge recombination speed, and PBI-BODIPY separation of charge speed
Only 10 times of charge recombination speed, therefore, in the case of illumination, the PTAC- with larger separation, compound difference
BODIPY and OMePTAC-BODIPY are more beneficial for the generation of free charge.
Finally illustrate, the above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted, this area is common
Other modifications or equivalent substitution that technical staff is made to technical scheme, without departing from technical solution of the present invention
Spirit and scope, all should cover among scope of the presently claimed invention.
Claims (7)
1. perylene tetracarboxylic acid-fluorine boron pyrroles's binary dye, the binary dye has following general structure I and formula II：
R in formula1And R2For alkyl, R3For alkoxy or hydrogen-based.
2. binary dye according to claim 1, it is characterised in that the R1For amyl group, R2For butyl, R3For methoxyl group
Or hydrogen-based.
3. the preparation method of the binary dye described in a kind of claim 1 or 2, it is characterised in that comprise the following steps：
(1) synthesis of the bromo- 7 Jia Yang Ji perylene tetracarboxylic acids esters of 1- Xiu perylene tetracarboxylic acids ester/1- and its derivative, its reaction equation is as follows：
(1-1) perylene tetracarboxylic acids esters and 1.0-20eq bromines, in the presence of 0.1eq-100eq alkali, reaction in a solvent obtains single bromine
Hua perylene tetracarboxylic acid esters；
The condition of (1-2) 1,7 2 bromine perylene tetracarboxylic acid ester and alcohol in 0.01eq-100eq metals copper catalyst, 0.1eq-100eq alkali
Under react in a solvent, obtain the bromo- 7 Wan Yang Ji perylene tetracarboxylic acid esters of 1-；
(2) synthesis of BODIPY borates：Bromination substrate B ODIPY reacts through suzuki miyaura, obtains BODIPY borates,
Reaction condition is in the presence of palladium catalyst, metallic catalyst, double (pinacol conjunctions) two boron and alkali is placed in solvent, control reaction
Temperature reacts 1-100h at 30-200 DEG C；Reaction equation is as follows：
(the preparation of 3) perylene tetracarboxylic acids-fluorine boron pyrroles's binary dye：
(3-1) is by step 1-1), 2) gained compound is coupled through Suzuki, the He Cheng Chu perylene tetracarboxylic acids-azole derivatives of fluorine boron two,
Its specific reaction condition is Xiuization perylene tetracarboxylic acid ester, metallic catalyst, BODIPY borates, alkali, is added in solvent, and control is anti-
Temperature is answered at 30-200 DEG C, 1-100h is reacted, it is purified to obtain target product；Reaction equation is as follows：
(3-2) is by step 1-2), 2) gained compound is coupled through Suzuki, He Cheng Chu perylene tetracarboxylic acids-fluorine boron pyrroles's binary dye,
Its specific reaction condition is Dan Xiu perylene diimides, metallic catalyst, BODIPY borates, alkali, is added in solvent, control reaction
Temperature reacts 1-100h at 30-200 DEG C, purified to obtain target product；Reaction equation is as follows：
R in formula1For amyl group, R2For butyl, R3 is methoxyl group or hydrogen-based.
4. preparation method according to claim 3, it is characterised in that step 1-1) conjunctions of the 1- Xiu perylene tetracarboxylic acid esters
Into the alkali is Na2CO3Or K2CO3；The solvent is tetrahydrofuran, dioxane, DMF or N, N diformazan
Yl acetamide.
5. preparation method according to claim 3, it is characterised in that step 1-2) described 1,7 Er Xiu perylene tetracarboxylic acid esters
Synthesis, the alkali is Na2CO3Or K2CO3, metal copper catalyst be CuI, CuBr or copper powder；The solvent is tetrahydrofuran, two
The ring of oxygen six, DMF or N, N dimethyl acetamide.
6. preparation method according to claim 3, it is characterised in that step 2) in the synthesis of the BODIPY borates,
Au catalyst is tetra-triphenylphosphine palladium, two chloro- bis-triphenyl phosphine palladiums, palladium or the double Diphenyl phosphino ferrocene dichloros of 1,1'-
Change palladium；Alkali is Na2CO3、K2CO3, NaOAc or KOAc；Solvent is toluene, dioxane, tetrahydrofuran or dimethyl sulfoxide (DMSO)；Instead
It is 0-150 DEG C to answer temperature.
7. preparation method according to claim 3, it is characterised in that step 3) reaction temperature is 0-150 DEG C；Reaction
Solvent is toluene, dioxane, DMSO, THF；Alkali is potassium acetate, sodium acetate, Na2CO3、K2CO3；The catalyst is Pd
(PPh3)4、Pd(PPh3)2Cl2、PdCl2(dppf)、PdCl2/PPh3Or palladium；The purification process is silica gel column chromatography, layer
Analyse liquid volume ratio dichloromethane/petroleum ether=1/20-5/1.
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