CN116397242A - Preparation method and application of film material based on naphthalene diazosulfide receptor structure - Google Patents
Preparation method and application of film material based on naphthalene diazosulfide receptor structure Download PDFInfo
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- CN116397242A CN116397242A CN202310378339.4A CN202310378339A CN116397242A CN 116397242 A CN116397242 A CN 116397242A CN 202310378339 A CN202310378339 A CN 202310378339A CN 116397242 A CN116397242 A CN 116397242A
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- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000000463 material Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims abstract description 46
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims abstract description 44
- PEIFSSHDFYVTMO-UHFFFAOYSA-N 3H-dithiadiazole naphthalene Chemical compound S1SNN=C1.C1=CC=CC2=CC=CC=C12 PEIFSSHDFYVTMO-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229930192474 thiophene Natural products 0.000 claims abstract description 23
- SSDDBKANEGGSRG-UHFFFAOYSA-N thiophene;tin Chemical compound [Sn].C=1C=CSC=1 SSDDBKANEGGSRG-UHFFFAOYSA-N 0.000 claims abstract description 22
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 20
- -1 1,2,5, 6-tetraminonaphthalene hydrochloride Chemical compound 0.000 claims abstract description 16
- 238000002484 cyclic voltammetry Methods 0.000 claims abstract description 16
- GCTFWCDSFPMHHS-UHFFFAOYSA-M Tributyltin chloride Chemical compound CCCC[Sn](Cl)(CCCC)CCCC GCTFWCDSFPMHHS-UHFFFAOYSA-M 0.000 claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 8
- 238000005859 coupling reaction Methods 0.000 claims abstract 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 91
- 238000006243 chemical reaction Methods 0.000 claims description 60
- 239000010408 film Substances 0.000 claims description 41
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 30
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 26
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 238000006116 polymerization reaction Methods 0.000 claims description 17
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 16
- OBISXEJSEGNNKL-UHFFFAOYSA-N dinitrogen-n-sulfide Chemical compound [N-]=[N+]=S OBISXEJSEGNNKL-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 13
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 12
- 239000012300 argon atmosphere Substances 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- 230000001681 protective effect Effects 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 238000005893 bromination reaction Methods 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000006619 Stille reaction Methods 0.000 claims description 5
- 239000010409 thin film Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 abstract description 7
- 230000004044 response Effects 0.000 abstract description 7
- 239000000047 product Substances 0.000 description 21
- 239000000243 solution Substances 0.000 description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- 239000012071 phase Substances 0.000 description 10
- 239000012265 solid product Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000001914 filtration Methods 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 238000002390 rotary evaporation Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 230000005526 G1 to G0 transition Effects 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000005562 fading Methods 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
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- 238000013461 design Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- FNQJDLTXOVEEFB-UHFFFAOYSA-N 1,2,3-benzothiadiazole Chemical group C1=CC=C2SN=NC2=C1 FNQJDLTXOVEEFB-UHFFFAOYSA-N 0.000 description 1
- 239000005964 Acibenzolar-S-methyl Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012490 blank solution Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
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- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/05—Heterocyclic compounds
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
- C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
- C07D513/04—Ortho-condensed systems
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Abstract
The invention provides a preparation method and application of a film material based on a naphthalene diazosulfide receptor structure, and relates to the technical field of organic photoelectric materials. The preparation method comprises the following steps: reacting 1,2,5, 6-tetraminonaphthalene hydrochloride with thionyl chloride to produce naphthalene dithiadiazole; brominating naphthalene dithiadiazole with N-bromosuccinimide to generate a brominated product NTz-2Br; reacting thiophene with tributyltin chloride to produce tin thiophene; the tin thiophene and NTz-2Br are subjected to a stinlle coupling reaction to generate NTz-2T; NTz-2T is taken as a monomer, and a cyclic voltammetry is adopted to prepare the film material based on the naphthalene diazosulfide receptor structure. The film material has fast response time, and is an electrochromic material with huge application prospect. Not only enriches the D-A-D type polymer electrochromic material system, but also has great reference significance for improving the electrochromic property of the polymer.
Description
Technical Field
The invention relates to the technical field of organic photoelectric materials, in particular to a preparation method and application of a film material based on a naphthalene di-thiadiazole receptor structure.
Background
Electrochromic refers to a phenomenon in which the optical properties of a material undergo a stable reversible change under the action of an external voltage, macroscopically representing a reversible change in color and transparency. The organic electrochromic material is synthesized and reported in a large quantity due to the advantages of easy modification of structure, adjustable color, quick response time, various processing modes and the like. The D-A-D type polymer electrochromic material can regulate the band gap of a monomer by regulating and controlling the electron cloud distribution between a donor and an acceptor, and finally, the color and the property of the polymer are adjustable. However, the receptor structural units commonly used at present are limited, so that the development of novel receptor structural units has great significance for improving the electrochromic property of the polymer. Through analysis and research on structural units of benzothiadiazole, researchers design and improve a novel receptor structural unit: naphthalene two and two thiadiazole. As a novel acceptor structure, it has the advantages of strong electron withdrawing ability, narrow energy gap, and strong planarity, but it is currently only applied to the field of solar cells.
Therefore, how to design and synthesize a D-A-D type molecule based on naphthalene dithiadiazole by taking naphthalene dithiadiazole as a receptor, and prepare a D-A-D structure electrochromic material with fast response time is a technical problem which needs to be solved by the technicians in the field.
Disclosure of Invention
The invention aims to provide a preparation method and application of a film material based on a naphthalene diazosulfide receptor structure, which are used for filling the blank of a D-A-D structure electrochromic material in the prior art.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a film material based on a naphthalene diazosulfide receptor structure, which comprises the following steps:
1) Reacting 1,2,5, 6-tetraminonaphthalene hydrochloride with thionyl chloride to produce naphthalene dithiadiazole;
2) Brominating the naphthalene diazosulfide generated in the step 1) with N-bromosuccinimide to generate a brominated product NTz-2Br;
3) Reacting thiophene with tributyltin chloride to produce tin thiophene;
4) Performing a stille coupling reaction on the tin-plated thiophene generated in the step 3) and NTz-2Br generated in the step 2) to generate NTz-2T;
5) NTz-2T is taken as a monomer, and a cyclic voltammetry is adopted to prepare the film material based on the naphthalene diazosulfide receptor structure.
Preferably, an organic solvent is further added in the reaction in the step 1), and the organic solvent comprises pyridine;
the addition ratio of the 1,2,5, 6-tetraminonaphthalene hydrochloride, the thionyl chloride and the organic solvent is 0.8 g-1.2 g: 0.75-1.0 mL: 20-30 mL;
the reaction time is 2-4 h, and the temperature is 70-80 ℃;
the reaction is carried out under a protective atmosphere comprising a nitrogen atmosphere or an argon atmosphere.
Preferably, the bromination reaction in step 2) is carried out as follows: adding naphthalene dithiadiazole and concentrated sulfuric acid into a reaction container, adding N-bromosuccinimide for 2-4 times in the first 1h, heating and refluxing, and adding N-bromosuccinimide and concentrated sulfuric acid in the next day and the third day respectively.
Preferably, the initial addition amount of the naphthalene dithiadiazole and the concentrated sulfuric acid is 1g: 20-30 mL;
the molar ratio of the total amount of N-bromosuccinimide added in the first 1h to the naphthalene dithiadiazole is 2-2.5: 1, a step of;
the mole ratio of N-bromosuccinimide and naphthalene dithiadiazole added in the next day and the third day is 0.8-1 independently: 1, a step of; the adding ratio of the concentrated sulfuric acid and the naphthalene dithiadiazole which are respectively added in the next day and the third day is 3-10 mL independently: 1g;
the heating reflux time is 65-75 hours; the temperature is 60-70 ℃;
the bromination reaction is carried out in the dark.
Preferably, the step of the reaction in step 3) is as follows: thiophene is dissolved in tetrahydrofuran, then n-hexane solution of n-butyllithium is added dropwise, the system temperature is kept still after the dropwise addition is completed, tributyltin chloride is added, and the mixture is naturally warmed to room temperature and stirred.
Preferably, the system temperature of the n-hexane solution in which the n-butyllithium is dropwise added is-75 ℃ to-80 ℃; the temperature of the maintaining system is kept stand for 1-2 h;
the molar ratio of thiophene, n-butyllithium and tributyltin chloride is 1:0.95 to 1.05:1.1 to 1.3; the addition ratio of tetrahydrofuran to thiophene is 10-15 mL:1g; the molar ratio of n-butyllithium to n-hexane is 1:1.4 to 1.8; the stirring time is 8-14 h;
the reaction is carried out under a protective atmosphere comprising a nitrogen atmosphere or an argon atmosphere.
Preferably, step 4) the step of the stille coupling reaction is as follows: NTz-2Br, tin thiophene, tetrakis (triphenylphosphine) palladium and N, N-dimethylformamide were mixed and heated to reflux.
Preferably, the molar ratio of NTz-2Br to tin thiophene is 1:2.7 to 3; the addition ratio of the N, N-dimethylformamide, the tetra (triphenylphosphine) palladium and the NTz-2Br is 90-110 mL: 15-25 mg:1g;
the temperature of the heating reflux is 110-130 ℃ and the time is 10-14 h;
the reaction is carried out under a protective atmosphere comprising a nitrogen atmosphere or an argon atmosphere.
Preferably, the preparation method in step 5) is as follows: dissolving NTz-2T in dichloromethane, adding tetrabutylammonium hexafluorophosphate, and performing electrochemical polymerization by a cyclic voltammetry to form a film;
wherein, the scanning speed is 90-110 mV/s, the voltage range is 0-1.5V, and the cycle number is 8-12;
the addition ratio of NTz-2T, tetrabutylammonium hexafluorophosphate and dichloromethane is 0.8-2 mmol:0.08 to 0.2mol:1L.
The invention also aims to provide an application of the film material based on the naphthalene diazosulfide receptor structure prepared by the preparation method in D-A-D electrochromic materials.
The invention has at least the following beneficial effects:
the naphthalene-Di-thiadiazole derivative benefits from a planar structure of naphthalene-Di-thiadiazole, takes naphthalene-Di-thiadiazole as a receptor, takes thiophene as a donor to construct a D-A-D structure monomer (NTz-2T), and shows a faster response time when a D-A-D structure polymer film is prepared by cyclic voltammetry polymerization, wherein the coloring time is 1.39s at 770nm, and the fading time is 0.48s; at 1100nm, the coloring time is 1.50s, the fading time is 0.58s, and the electrochromic material has great application prospect. The method not only enriches the D-A-D type polymer electrochromic material system, but also has great reference significance for improving the electrochromic property of the polymer.
Drawings
FIG. 1 is a synthetic route for preparing D-A-D type derivatives NTz-2T based on the naphthalene diazosulfide receptor structure according to example 1 of the present invention;
FIG. 2 is a graph of cyclic voltammetry polymerization of a thin film material based on a naphthalene diazosulfide acceptor structure prepared in example 1 of the present invention;
FIG. 3 is a graph showing the UV-visible absorption spectra of a film material based on the naphthalene diazosulfide acceptor structure prepared in example 1 of the present invention at different voltages;
FIG. 4 is a graph showing the response time of the film material based on the naphthalene diazosulfide acceptor structure prepared in example 1 of the present invention at different wavebands.
Detailed Description
The invention provides a preparation method of a film material based on a naphthalene diazosulfide receptor structure, which comprises the following steps:
1) Reacting 1,2,5, 6-tetraminonaphthalene hydrochloride with thionyl chloride to produce naphthalene dithiadiazole;
2) Brominating the naphthalene diazosulfide generated in the step 1) with N-bromosuccinimide to generate a brominated product NTz-2Br;
3) Reacting thiophene with tributyltin chloride to produce tin thiophene;
4) Performing a stille coupling reaction on the tin-plated thiophene generated in the step 3) and NTz-2Br generated in the step 2) to generate NTz-2T;
5) NTz-2T is taken as a monomer, and a cyclic voltammetry is adopted to prepare the film material based on the naphthalene diazosulfide receptor structure.
In the invention, an organic solvent is also required to be added in the reaction in the step 1), and the organic solvent comprises pyridine;
the addition ratio of the 1,2,5, 6-tetralin hydrochloride, the thionyl chloride and the organic solvent is preferably 0.8g to 1.2g: 0.75-1.0 mL:20 to 30mL, more preferably 0.9g to 1.1g: 0.8-0.95 mL:22 to 28mL, more preferably 1g to 1.1g: 0.85-0.9 mL: 24-26 mL;
the reaction time is preferably 2 to 4 hours, more preferably 2.5 to 3.5 hours, still more preferably 2.8 to 3.2 hours; the temperature is preferably 70 to 80 ℃, more preferably 72 to 78 ℃, still more preferably 74 to 76 ℃;
the reaction is carried out under a protective atmosphere comprising a nitrogen atmosphere or an argon atmosphere.
In the present invention, after the reaction in step 1), a post-treatment step is further included: extracting the reaction system by using a solvent, concentrating the separated organic phase, and removing the solvent by rotary evaporation after column chromatography separation to obtain naphthalene di-thiadiazole (NTz);
the solvent used for extraction is preferably dichloromethane and water, and the volume ratio of dichloromethane to water is 1:1-2, and more preferably 1:1.5; the number of extraction is preferably 2 to 4, more preferably 3; the drying agent used for removing water is preferably anhydrous sodium sulfate; the mobile phase used for column chromatography separation is preferably petroleum ether and dichloromethane, and the volume ratio of petroleum ether to dichloromethane is preferably 1-2: 1, more preferably 1.5:1, a step of;
the structural formula of the naphthalene diazosulfide (NTz) is as follows:
in the present invention, the bromination reaction in step 2) is carried out as follows: adding naphthalene dithiadiazole and concentrated sulfuric acid into a reaction container, and adding N-bromosuccinimide preferably for 2-4 times in the first 1h, more preferably for 3 times; then heating and refluxing, and adding N-bromosuccinimide and concentrated sulfuric acid on the second day and the third day respectively.
In the present invention, the initial addition amount of the naphthalene dithiadiazole and concentrated sulfuric acid is preferably 1g:20 to 30mL, more preferably 1g:22 to 28mL, more preferably 1g: 24-26 mL;
the molar ratio of the total amount of N-bromosuccinimide to the naphthalene dithiadiazole added in the first 1h is preferably 2 to 2.5:1, more preferably 2.1 to 2.4:1, more preferably 2.2 to 2.3:1, a step of;
the molar ratio of N-bromosuccinimide to naphthalene dithiadiazole added in the next day and the third day is preferably 0.8-1: 1, more preferably 0.9:1, a step of; the addition ratio of the concentrated sulfuric acid and the naphthalene dithiadiazole which are respectively added in the next day and the third day is independently preferably 3-10 mL:1g, more preferably 4 to 9mL:1g, more preferably 6 to 8mL:1g;
the heating reflux time is preferably 65 to 75 hours, more preferably 68 to 74 hours, and even more preferably 72 hours; the temperature is preferably 60 to 70 ℃, more preferably 62 to 68 ℃, still more preferably 64 to 66 ℃;
the bromination reaction is carried out in the dark.
In the present invention, after the reaction in step 2), a post-treatment step is further included: pouring the reaction system into ice water after the reaction is finished, separating out orange-red solid, carrying out suction filtration and separation, and washing and drying to obtain a brominated product NTz-2Br;
the washing process is preferably to wash sequentially with deionized water, ethanol and tetrahydrofuran;
the brominated product NTz-2Br has the following structural formula:
in the present invention, the reaction in step 3) is carried out as follows: thiophene is dissolved in tetrahydrofuran, then n-hexane solution of n-butyllithium is added dropwise, the system temperature is kept still after the dropwise addition is completed, tributyltin chloride is added, and the mixture is naturally warmed to room temperature and stirred.
In the invention, the system temperature of the n-hexane solution dropwise added with the n-butyllithium is preferably-75 ℃ to-80 ℃, more preferably-76 ℃ to-79 ℃, and even more preferably-78 ℃; the time for keeping the temperature of the system to stand is preferably 1 to 2 hours, more preferably 1.5 hours;
the molar ratio of thiophene, n-butyllithium and tributyltin chloride is preferably 1:0.95 to 1.05:1.1 to 1.3, more preferably 1:0.98 to 1.02:1.15 to 1.25, more preferably 1:1:1.2; the addition ratio of tetrahydrofuran and thiophene is preferably 10-15 mL:1g, more preferably 11 to 14mL:1g, more preferably 12 to 13mL:1g; the molar ratio of n-butyllithium to n-hexane is preferably 1:1.4 to 1.8, more preferably 1:1.5 to 1.7, more preferably 1:1.5 to 1.6; the stirring time is preferably 8 to 14 hours, more preferably 9 to 12 hours, and still more preferably 10 to 11 hours;
the reaction is carried out under a protective atmosphere comprising a nitrogen atmosphere or an argon atmosphere.
In the present invention, after the reaction in step 3), a post-treatment step is further included: after the reaction is finished, taking neutral aluminum oxide as a stationary phase and methylene dichloride as a mobile phase, collecting eluent containing a target compound, and removing a solvent by rotary evaporation to obtain tin thiophene;
the structural formula of the tin thiophene is as follows:
in the present invention, the step of the stille coupling reaction of step 4) is as follows: NTz-2Br, tin thiophene, tetrakis (triphenylphosphine) palladium and N, N-dimethylformamide were mixed and heated to reflux.
In the present invention, the molar ratio of NTz-2Br to tin thiophene is preferably 1:2.7 to 3, more preferably 1:2.8 to 2.9, more preferably 1:2.8; the addition ratio of N, N-dimethylformamide, tetrakis (triphenylphosphine) palladium and NTz-2Br is preferably 90 to 110mL: 15-25 mg:1g, more preferably 95 to 105mL: 16-14 mg:1g, more preferably 98-102 mL: 18-22 mg:1g;
the temperature of the heating reflux is preferably 110 to 130 ℃, more preferably 115 to 125 ℃, and still more preferably 118 to 112 ℃; the time is preferably 10 to 14 hours, more preferably 11 to 13 hours, and still more preferably 12 hours;
the reaction is carried out under a protective atmosphere comprising a nitrogen atmosphere or an argon atmosphere.
In the present invention, after the reaction in step 4), a post-treatment step is further included: the reaction solution was cooled to room temperature, poured into methanol, and the precipitated red solid product was collected by filtration. Separating by column chromatography with petroleum ether and dichloromethane as mobile phase, and removing solvent by rotary evaporation to obtain target product NTz-2T;
the volume ratio of petroleum ether and methylene dichloride in the mobile phase is preferably 3.5-5.5: 1, more preferably 4 to 5:1, still more preferably 4.5:1;
the structural formula of the target product NTz-2T is as follows:
in the present invention, the preparation method described in step 5) is as follows: dissolving NTz-2T in dichloromethane, adding tetrabutylammonium hexafluorophosphate, and performing electrochemical polymerization by a cyclic voltammetry to form a film;
among them, the scanning speed is preferably 90 to 110mV/s, more preferably 95 to 105mV/s, still more preferably 98 to 102mV/s; the voltage range is preferably 0 to 1.5V, more preferably 0.5 to 1.2V, and still more preferably 0.8 to 1V; the number of circulation turns is preferably 8 to 12, more preferably 9 to 11, and still more preferably 10;
the addition ratio of NTz-2T, tetrabutylammonium hexafluorophosphate and dichloromethane is preferably 0.8-2 mmol:0.08 to 0.2mol:1L, more preferably 1 to 1.8mmol:0.1 to 0.18mol:1L, more preferably 1.2 to 1.6mmol:0.12 to 0.16mol:1L.
In the present invention, step 5) further comprises cleaning the film in methylene chloride after the polymerization is completed to remove the surface unpolymerized monomers or oligomers and the residual electrolyte.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
1) Synthesis of NTz
To the reaction flask was added 1,2,5, 6-tetralin hydrochloride (0.567 g) under nitrogen protection followed by 15mL pyridine and thionyl chloride (0.45 mL,2.31 mmol). Stirred and heated to 75℃and reacted at 75℃for 3h. After the reaction was completed, the reaction mixture was cooled to room temperature, the reaction mixture was extracted 2 times with a mixed solution of dichloromethane and water (dichloromethane and water in a volume ratio of 1:1.5), an organic phase was collected, the solid product was purified by using a chromatography column using (petroleum ether) PE (dichloromethane) dcm=1.5:1, and an off-white product, naphthalene dithiadiazole NTz, was obtained.
1 HNMR(500MHz,CDCl 3 )δ(ppm):8.96(d,J＝9.1Hz,1H),8.23(d,J＝9.1Hz,1H).
2) Synthesis of NTz-2Br
Naphthalene two thiophene two (0.245 g,1 mmol) and 5mL concentrated sulfuric acid were added sequentially to the reaction flask under dark conditions, and the mixture was heated to 65℃to react for 72h. NBS (0.225 mmol) was added 3 times over the first 1h with a total mass of 0.40g, and 0.15g NBS (0.843 mmol) and 1mL of concentrated sulfuric acid were added for the second and third days. After the reaction is finished, pouring the reaction solution into ice water, at the moment, separating out orange-red solid, filtering the solution, washing a filter cake with water, ethanol and tetrahydrofuran in sequence, and drying to obtain a brominated product NTz-2Br, wherein the product is basically insoluble in any solvent, so that the product cannot be subjected to the next characterization and is directly used for the next reaction.
3) Synthesis of tin thiophene
Thiophene (1.0 g,11.88 mmol) was dissolved in 15mL of ultra-dry tetrahydrofuran, then 7.42mL of n-hexane (1.6M) of n-butyllithium was added dropwise at-78deg.C, stirred for 1h with heat preservation, then tributyltin chloride (14.3 mmol) was added, followed by warming to room temperature and stirring for 12h. After the reaction is finished, taking aluminum oxide as a stationary phase and methylene dichloride as a mobile phase, collecting eluent containing a target compound, and removing a solvent by rotary evaporation to obtain liquid tin thiophene.
4) Synthesis of NTz-2T
The brominated product NTz-2Br (0.31 g,0.78 mmol), tin thiophene (2.19 mmol) and 5mg of tetrakis (triphenylphosphine) palladium were added to the reaction flask under nitrogen, 30mL of ultra-dry DMF was added, and the mixture was refluxed at 120℃for 12h. The reaction solution was cooled to room temperature, poured into methanol, and the precipitated red solid product was collected by filtration. The solid product was purified using a chromatographic column using a mobile phase ratio of PE: dcm=5:1 to give a red solid.
1 HNMR(400MHz,CDCl 3 )δppm):9.13(s,2H),8.33(d,J＝3.7Hz,2H),7.55(d,J＝5.1Hz,2H),7.29(d,J＝4.6Hz,2H).
5) Cyclic voltammetry method for preparing film material based on naphthalene diazosulfide receptor structure
NTz-2T (0.01 mmol) and tetrabutylammonium hexafluorophosphate (1 mmol) were added to a 10mL volumetric flask, the volume was determined with chromatographic grade dichloromethane, and after complete dissolution, electrochemical polymerization was performed by 50kHz ultrasound for 5 min. ITO glass (0.9 x 4 cm) is used as a working electrode, a platinum wire is used as a counter electrode, an Ag/AgCl electrode is used as a reference electrode, a cyclic voltammetry polymerization film is adopted, the scanning speed is 100mV/s, the voltage range is 0-1.5V, and the cycle number is 10. After the polymerization, the electrolyte and oligomer on the surface of the film are washed off by using chromatographic grade dichloromethane. FIG. 2 is a graph showing cyclic voltammetry polymerization when synthesizing a thin film material, from which: with the increase of the polymerization number, the peak current is also increasing, which indicates that the monomer is successfully polymerized and the generated film is well attached to the surface of the ITO glass.
Example 2
1) Synthesis of NTz
To the reaction flask was added 1,2,5, 6-tetralin hydrochloride (0.8 g) under nitrogen protection, followed by 20mL of pyridine and thionyl chloride (0.75 mL). Stirred and heated to 70℃and reacted at 70℃for 4h. After the reaction was completed, the reaction mixture was cooled to room temperature, the reaction mixture was extracted 2 times with a mixed solution of dichloromethane and water (dichloromethane and water in a volume ratio of 1:1), an organic phase was collected, the solid product was purified by using a chromatography column using (petroleum ether) PE (dichloromethane) dcm=1:1, and an off-white product, naphthalene dithiadiazole NTz, was obtained.
2) Synthesis of NTz-2Br
Naphthalene two thiophene two (1 g,4.08 mmol) and 20mL concentrated sulfuric acid were added sequentially to the reaction flask under dark conditions, and the mixture was heated to 60℃to react for 75h. NBS (8.2 mmol) was added in 2 portions over the first 1h with a total mass of 1.46g, and 0.582g NBS (3.27 mmol) and 3mL of concentrated sulfuric acid were added for the second and third days. After the reaction is finished, pouring the reaction solution into ice water, at the moment, separating out orange-red solid, filtering the solution, washing a filter cake with water, ethanol and tetrahydrofuran in sequence, and drying to obtain a brominated product NTz-2Br, wherein the product is basically insoluble in any solvent, so that the product cannot be subjected to the next characterization and is directly used for the next reaction.
3) Synthesis of tin thiophene
Thiophene (1.0 g,11.88 mmol) was dissolved in 10mL of ultra-dry tetrahydrofuran, then 8.07mL of n-hexane (1.4M) of n-butyllithium was added dropwise at-75℃and stirred for 1.5h with heat preservation, then tributyltin chloride (13.07 mmol) was added, followed by warming to room temperature and stirring for 10h. After the reaction is finished, taking aluminum oxide as a stationary phase and methylene dichloride as a mobile phase, collecting eluent containing a target compound, and removing a solvent by rotary evaporation to obtain liquid tin thiophene.
4) Synthesis of NTz-2T
To the reaction flask were added under nitrogen protection the brominated product NTz-2Br (0.402 g,1 mmol), tin thiophene (2.70 mmol) and 8.04mg of tetrakis (triphenylphosphine) palladium, 36.2mL of ultra-dry DMF was added, and the mixture was refluxed at 110℃for 14h. The reaction solution was cooled to room temperature, poured into methanol, and the precipitated red solid product was collected by filtration. The solid product was purified using a chromatographic column using a mobile phase ratio of PE: dcm=4:1 to give a red solid.
1 HNMR(400MHz,CDCl 3 )δppm):9.13(s,2H),8.33(d,J＝3.7Hz,2H),7.55(d,J＝5.1Hz,2H),7.29(d,J＝4.6Hz,2H).
5) Cyclic voltammetry method for preparing film material based on naphthalene diazosulfide receptor structure
NTz-2T (0.008 mmol) and tetrabutylammonium hexafluorophosphate (2 mmol) were put into a 10mL volumetric flask, the volume was fixed with chromatographic grade dichloromethane, and after complete dissolution, electrochemical polymerization was performed by ultrasonic at 50kHz for 5 min. ITO glass (0.9 x 4 cm) is used as a working electrode, a platinum wire is used as a counter electrode, an Ag/AgCl electrode is used as a reference electrode, a cyclic voltammetry polymerization film is adopted, the scanning speed is 90mV/s, the voltage range is 0-1.5V, and the number of circulation turns is 8. After the polymerization, the electrolyte and oligomer on the surface of the film are washed off by using chromatographic grade dichloromethane.
Example 3
1) Synthesis of NTz
To the reaction flask was added 1,2,5, 6-tetralin hydrochloride (3.60 mmol) under nitrogen protection, followed by 30mL of pyridine and thionyl chloride (1 mL). Stirred and heated to 80℃and reacted at 80℃for 2.5h. After the reaction was completed, the reaction mixture was cooled to room temperature, the reaction mixture was extracted 4 times with a mixed solution of dichloromethane and water (dichloromethane and water in a volume ratio of 1:2), and the organic phase was collected, and the solid product was purified by using a chromatography column using (petroleum ether) PE (dichloromethane) dcm=2:1 to obtain an off-white product, naphthalene dithiadiazole NTz.
2) Synthesis of NTz-2Br
Naphthalene two thiophene two (1.00 g,4.08 mmol) and 30mL concentrated sulfuric acid were added sequentially to the reaction flask under dark condition, and heated to 70 ℃ for reaction for 65h. NBS (10.17 mmol) was added in a total mass of 1.81g 4 times over the first 1h, and 0.726g NBS (4.08 mmol) and 10mL of concentrated sulfuric acid were added for the second and third days. After the reaction is finished, pouring the reaction solution into ice water, at the moment, separating out orange-red solid, filtering the solution, washing a filter cake with water, ethanol and tetrahydrofuran in sequence, and drying to obtain a brominated product NTz-2Br, wherein the product is basically insoluble in any solvent, so that the product cannot be subjected to the next characterization and is directly used for the next reaction.
3) Synthesis of tin thiophene
Thiophene (1 g,11.88 mmol) was dissolved in 10mL of ultra-dry tetrahydrofuran, then 6.93mL of n-hexane (1.8M) of n-butyllithium was added dropwise at-80℃and stirred for 2 hours with heat preservation, then tributyltin chloride (15.4 mmol) was added, followed by warming to room temperature and stirring for 14 hours. After the reaction is finished, taking aluminum oxide as a stationary phase and methylene dichloride as a mobile phase, collecting eluent containing a target compound, and removing a solvent by rotary evaporation to obtain liquid tin thiophene.
4) Synthesis of NTz-2T
To the reaction flask were added under nitrogen protection the brominated product NTz-2Br (0.402 g,1 mmol), tin thiophene (3.0 mmol) and 10.05mg of tetrakis (triphenylphosphine) palladium, 44.22mL of ultra-dry DMF was added, and the mixture was refluxed at 130℃for 10h. The reaction solution was cooled to room temperature, poured into methanol, and the precipitated red solid product was collected by filtration. The solid product was purified using a chromatographic column using a mobile phase ratio of PE: dcm=5.5:1 to give a red solid.
5) Cyclic voltammetry method for preparing film material based on naphthalene diazosulfide receptor structure
NTz-2T (0.02 mmol) and tetrabutylammonium hexafluorophosphate (0.8 mmol) were added to a 10mL volumetric flask, the volume was determined with chromatographic grade dichloromethane, and after complete dissolution, electrochemical polymerization was performed at 50kHz for 5 min. ITO glass (0.9 x 4 cm) is used as a working electrode, a platinum wire is used as a counter electrode, an Ag/AgCl electrode is used as a reference electrode, a cyclic voltammetry polymerization film is adopted, the scanning speed is 110mV/s, the voltage range is 0-1.5V, and the cycle number is 12. After the polymerization, the electrolyte and oligomer on the surface of the film are washed off by using chromatographic grade dichloromethane.
Performance testing
Tetrabutylammonium hexafluorophosphate (0.387 g,1 mmol) was added to a 10mL volumetric flask, the volume was fixed with chromatographic grade acetonitrile, it was used as a blank solution, ITO glass was coated on the thin film material based on the naphthalene dithiadiazole acceptor structure prepared in example 1 as a working electrode, a platinum sheet was a counter electrode, an Ag/AgCl electrode was a reference electrode, and electrochemical, optical and electrochromic performance test was performed in combination with an ultraviolet-visible spectrophotometer.
FIG. 3 is a graph of the UV-visible absorption spectra of the film material at various voltages. As can be seen from the figure: when 0V voltage is applied to the film material, the film material has the highest absorption peak at 570nm, and the film is purple; and when a voltage of 1.5V is applied, it reaches full absorption in the visible range, at which time the film appears black.
FIG. 4 is a graph showing the response time of the film material based on the naphthalene diazosulfide acceptor structure prepared in example 1 of the present invention at different wavebands. As can be seen from the figure: thanks to the planar structure of the naphthalene diazosulfide, the film exhibits a faster response time, a coloration time of 1.39s at 770nm and a fade time of 0.48s. At 1100nm, the coloring time is 1.50s, the fading time is 0.58s, and the material is a novel electrochromic material with great application prospect.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A method for preparing a film material based on a naphthalene diazosulfide receptor structure, which is characterized by comprising the following steps:
1) Reacting 1,2,5, 6-tetraminonaphthalene hydrochloride with thionyl chloride to produce naphthalene dithiadiazole;
2) Brominating the naphthalene diazosulfide generated in the step 1) with N-bromosuccinimide to generate a brominated product NTz-2Br;
3) Reacting thiophene with tributyltin chloride to produce tin thiophene;
4) Performing a stille coupling reaction on the tin-plated thiophene generated in the step 3) and NTz-2Br generated in the step 2) to generate NTz-2T;
5) NTz-2T is taken as a monomer, and a cyclic voltammetry is adopted to prepare the film material based on the naphthalene diazosulfide receptor structure.
2. The method for preparing a film material based on a naphthalene diazosulfide acceptor structure according to claim 1, wherein an organic solvent is added in the reaction in step 1), and the organic solvent comprises pyridine;
the addition ratio of the 1,2,5, 6-tetraminonaphthalene hydrochloride, the thionyl chloride and the organic solvent is 0.8 g-1.2 g: 0.75-1.0 mL: 20-30 mL;
the reaction time is 2-4 h, and the temperature is 70-80 ℃;
the reaction is carried out under a protective atmosphere comprising a nitrogen atmosphere or an argon atmosphere.
3. A method for preparing a film material based on a naphthalene diazosulfide acceptor structure according to claim 1 or 2, wherein the bromination reaction in step 2) is as follows: adding naphthalene dithiadiazole and concentrated sulfuric acid into a reaction container, adding N-bromosuccinimide for 2-4 times in the first 1h, heating and refluxing, and adding N-bromosuccinimide and concentrated sulfuric acid in the next day and the third day respectively.
4. The method for preparing a film material based on a naphthalene diazosulfide receptor structure according to claim 3, wherein the initial addition amount of naphthalene diazosulfide and concentrated sulfuric acid is 1g: 20-30 mL;
the molar ratio of the total amount of N-bromosuccinimide added in the first 1h to the naphthalene dithiadiazole is 2-2.5: 1, a step of;
the mole ratio of N-bromosuccinimide and naphthalene dithiadiazole added in the next day and the third day is 0.8-1 independently: 1, a step of; the adding ratio of the concentrated sulfuric acid and the naphthalene dithiadiazole which are respectively added in the next day and the third day is 3-10 mL independently: 1g;
the heating reflux time is 65-75 hours; the temperature is 60-70 ℃;
the bromination reaction is carried out in the dark.
5. A method for preparing a film material based on a naphthalene diazosulfide acceptor structure according to claim 3, wherein the reaction in step 3) is as follows: thiophene is dissolved in tetrahydrofuran, then n-hexane solution of n-butyllithium is added dropwise, the system temperature is kept still after the dropwise addition is completed, tributyltin chloride is added, and the mixture is naturally warmed to room temperature and stirred.
6. The method for preparing a film material based on a naphthalene diazosulfide receptor structure according to claim 5, wherein the system temperature of the n-hexane solution of the dropwise addition of n-butyllithium is-75 ℃ to-80 ℃; the temperature of the maintaining system is kept stand for 1-2 h;
the molar ratio of thiophene, n-butyllithium and tributyltin chloride is 1:0.95 to 1.05:1.1 to 1.3; the addition ratio of tetrahydrofuran to thiophene is 10-15 mL:1g; the molar ratio of n-butyllithium to n-hexane is 1:1.4 to 1.8; the stirring time is 8-14 h;
the reaction is carried out under a protective atmosphere comprising a nitrogen atmosphere or an argon atmosphere.
7. A method for preparing a thin film material based on a naphthalene diazosulfide receptor structure according to claim 1,2 or 5, characterized in that the step of the stinlle coupling reaction of step 4) is as follows: NTz-2Br, tin thiophene, tetrakis (triphenylphosphine) palladium and N, N-dimethylformamide were mixed and heated to reflux.
8. The method for preparing a film material based on a naphthalene diazosulfide acceptor structure according to claim 7, wherein the molar ratio of NTz-2Br to tin thiophene is 1:2.7 to 3; the addition ratio of the N, N-dimethylformamide, the tetra (triphenylphosphine) palladium and the NTz-2Br is 90-110 mL: 15-25 mg:1g;
the temperature of the heating reflux is 110-130 ℃ and the time is 10-14 h;
the reaction is carried out under a protective atmosphere comprising a nitrogen atmosphere or an argon atmosphere.
9. The method for preparing a film material based on a naphthalene diazosulfide receptor structure according to claim 7, wherein the preparation method in the step 5) is as follows: dissolving NTz-2T in dichloromethane, adding tetrabutylammonium hexafluorophosphate, and performing electrochemical polymerization by a cyclic voltammetry to form a film;
wherein, the scanning speed is 90-110 mV/s, the voltage range is 0-1.5V, and the cycle number is 8-12;
the addition ratio of NTz-2T, tetrabutylammonium hexafluorophosphate and dichloromethane is 0.8-2 mmol:0.08 to 0.2mol:1L.
10. Use of a film material based on a naphthalene diazosulfide receptor structure prepared by the preparation method of any one of claims 1 to 9 in a D-a-D electrochromic material.
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