CN114634546B - High-luminous-power electrochromic material from red to near infrared and preparation method thereof - Google Patents
High-luminous-power electrochromic material from red to near infrared and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 238000003333 near-infrared imaging Methods 0.000 title description 2
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 claims abstract description 55
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 54
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 42
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 33
- 235000012000 cholesterol Nutrition 0.000 claims abstract description 32
- -1 formamidophenylacetonitrile Chemical compound 0.000 claims abstract description 31
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000047 product Substances 0.000 claims abstract description 26
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 24
- PDQRQJVPEFGVRK-UHFFFAOYSA-N 2,1,3-benzothiadiazole Chemical compound C1=CC=CC2=NSN=C21 PDQRQJVPEFGVRK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 18
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 14
- PAMBVPQLDDXPCQ-UHFFFAOYSA-N boric acid;n,n-diphenylaniline Chemical compound OB(O)O.C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 PAMBVPQLDDXPCQ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000012065 filter cake Substances 0.000 claims abstract description 9
- 238000002386 leaching Methods 0.000 claims abstract description 8
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 8
- 238000004440 column chromatography Methods 0.000 claims abstract description 5
- 238000005303 weighing Methods 0.000 claims abstract description 5
- 239000013067 intermediate product Substances 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000010025 steaming Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 41
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 39
- 239000007787 solid Substances 0.000 claims description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 239000005964 Acibenzolar-S-methyl Substances 0.000 claims description 12
- 230000002194 synthesizing effect Effects 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 9
- 238000004020 luminiscence type Methods 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 7
- 239000003480 eluent Substances 0.000 claims description 5
- 238000001514 detection method Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 230000008859 change Effects 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- QOVUQHJLIWOBNB-UHFFFAOYSA-N C1=CC=CC=C1[P](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 Chemical compound C1=CC=CC=C1[P](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 QOVUQHJLIWOBNB-UHFFFAOYSA-N 0.000 abstract 1
- 239000000523 sample Substances 0.000 abstract 1
- 230000003068 static effect Effects 0.000 description 17
- 239000000243 solution Substances 0.000 description 12
- 239000002904 solvent Substances 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 238000002390 rotary evaporation Methods 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000002189 fluorescence spectrum Methods 0.000 description 4
- 239000007850 fluorescent dye Substances 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- FNQJDLTXOVEEFB-UHFFFAOYSA-N 1,2,3-benzothiadiazole Chemical compound C1=CC=C2SN=NC2=C1 FNQJDLTXOVEEFB-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000539 dimer Substances 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- USLPZCOPYRKTGY-UHFFFAOYSA-N 2-(2-phenylethenyl)benzonitrile Chemical compound N#CC1=CC=CC=C1C=CC1=CC=CC=C1 USLPZCOPYRKTGY-UHFFFAOYSA-N 0.000 description 1
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- 150000001454 anthracenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 238000012984 biological imaging Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- OKZIUSOJQLYFSE-UHFFFAOYSA-N difluoroboron Chemical class F[B]F OKZIUSOJQLYFSE-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000008423 fluorobenzenes Chemical class 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 238000003958 fumigation Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000004897 thiazines Chemical class 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J43/00—Normal steroids having a nitrogen-containing hetero ring spiro-condensed or not condensed with the cyclopenta(a)hydrophenanthrene skeleton
- C07J43/003—Normal steroids having a nitrogen-containing hetero ring spiro-condensed or not condensed with the cyclopenta(a)hydrophenanthrene skeleton not condensed
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/008—Triarylamine dyes containing no other chromophores
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
- G01L1/00—Measuring force or stress, in general
- G01L1/24—Measuring force or stress, in general by measuring variations of optical properties of material when it is stressed, e.g. by photoelastic stress analysis using infrared, visible light, ultraviolet
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—Condensed systems
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
- C09K2211/1051—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms with sulfur
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- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Luminescent Compositions (AREA)
- Steroid Compounds (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
The invention belongs to the field of high luminous power electrochromic materials, and provides a red to near infrared high luminous power electrochromic material and a preparation method thereof, wherein the preparation method comprises the following steps of 1, weighing 7-bromo-4-aldehyde benzo [ c ] [1,2,5] thiadiazole, triphenylamine boric acid, tetraphenylphosphorus palladium and sodium carbonate, preparing sodium carbonate into sodium carbonate aqueous solution, and dissolving the raw materials in chromatographic toluene and tetrahydrofuran; then extracting, filtering, separating by column chromatography and rotary steaming to obtain 7-triphenylamine-4-aldehyde benzo [ c ] [1,2,5] thiadiazole; step 2, dissolving an intermediate product, cholesterol formamidophenylacetonitrile and sodium methoxide in ethanol; and leaching the filter cake with ethanol for 3 times, and drying to obtain red powder, namely the target product. The invention has larger force-induced ratio color change, can be used as a fluorescent pressure sensing probe, and has the following characteristics: the fluorescent material has high fluorescent efficiency (44.3%), simple synthesis, capability of quantitatively determining the relation between pressure and emission wavelength and large color change range, and has great application potential on a pressure sensing system.
Description
Technical Field
The invention belongs to the field of high-luminous-force electrochromic materials, and particularly relates to a preparation method of a red-to-near-infrared high-luminous-force electrochromic material.
Background
In recent years, the organic near infrared (680-900 nm) fluorescent dye has wide application prospect in the fields of biological imaging, pressure sensing, infrared camouflage, anti-counterfeiting detection, fluorescent identification and the like due to the advantages of strong penetrability, strong anti-interference capability, good sensitivity and the like.
Several types of near infrared fluorescent probes have been reported so far, and these materials can be classified into: stilbene nitriles, difluoroboron compounds, tetraphenyl compounds, aromatic acid cyanines, thiazines, BODIPY compounds, and the like. As reported in (chem. Eur. J.,2014,21,2474-2479), a compound of electron-withdrawing structure pCN-TPA with stilbene nitrile as core, which exhibits luminescence of 508nm under initial normal pressure, can gradually red shift to 618nm under the action of static pressure, red shift to 110nm, and can be restored to the initial state after the static pressure is released. (chem. Commun.,2016,52,3836-3839) a cyano-substituted stilbene derivative structure CzCNDSB is synthesized, the initial luminescence is 529nm, the luminescence can be red-shifted by 155nm to 684nm under the action of external static pressure, the change from green to dark red is realized, and the luminescence can be restored to the initial state after the static pressure is removed. (Angew. Chem. Int. Ed.,2020,59,15267-15267) adopts a eutectic strategy, and the anthracene derivative and the fluorobenzene derivative are subjected to solvent fumigation to obtain eutectic, so that 554nm luminescence can be realized in an initial state, and 92nm to 646nm (green to red transition) can be shifted in red under the action of static pressure.
However, static pressure electrochromic materials with high fluorescence quantum efficiency and in the near infrared region are also relatively few. The key to constructing a high contrast near infrared deep red to near infrared discolouration range is to inhibit pi-pi interactions between molecules under pressure.
Disclosure of Invention
The invention aims to solve the problems recorded in the background technology and provides a preparation method of a red-to-near infrared high-luminous-power electrochromic material.
In order to achieve the above purpose, the invention adopts the following technical scheme: a method for preparing a red to near infrared high luminous intensity electrochromic material, which comprises the following steps:
step 1, synthesizing an intermediate 7-triphenylamine-4-aldehyde benzo [ c ] [1,2,5] thiadiazole:
weighing 7-bromo-4-aldehyde benzo [ c ] [1,2,5] thiadiazole, triphenylamine boric acid, tetra-triphenylphosphonium palladium and sodium carbonate, preparing sodium carbonate into sodium carbonate solution, and dissolving the raw materials into chromatographic toluene and tetrahydrofuran; under the protection of nitrogen atmosphere, refluxing and stirring for reaction, confirming the reaction progress through a spot plate when a large amount of red solid particles are precipitated, and stopping the reaction if the reaction is complete; then extracting, filtering, separating by column chromatography and rotary steaming to obtain red powder, namely the 7-triphenylamine-4-aldehyde benzo [ c ] [1,2,5] thiadiazole;
step 2, synthesizing a target product:
dissolving an intermediate product, cholesterol formamidophenylacetonitrile and sodium methoxide in ethanol; stirring to react at 60 ℃ under the protection of nitrogen atmosphere, and stopping the reaction when a large amount of solid particles are separated out; and then the ethanol solution of the product is placed into a refrigerator for cooling and precipitation, and after solid precipitation is completed, the filtering is carried out, the filter cake obtained by filtering is leached with ethanol for 3 times, and the red powder is obtained after drying, namely the target product.
The target product is a near infrared region color-changing dye benzothiadiazole cholesterol formamidophenylacetonitrile derivative, and the chemical formula is as follows: c (C) 61 H 67 N 5 O 2 S。
In a preferred embodiment of the present invention, the molar ratio of 7-bromo-4-aldyl benzo [ c ] [1,2,5] thiadiazole to triphenylamine boric acid is from 1:1 to 1:1.5; 7-bromo-4-aldehyde benzo [ c ] [1,2,5] thiadiazole: sodium carbonate: toluene: the dosage ratio of tetrahydrofuran is as follows: 10mmol, 0.8-1.2mmol, 50-60ml, 30-40ml, wherein the concentration of the sodium carbonate solution is 3mol/L.
In a preferred embodiment of the invention, in step 1, the reflux stirring reaction time is 12-24 hours and the reaction temperature is 80-100 ℃.
In a preferred embodiment of the invention, the extract is methylene chloride and the leacheate of column chromatography is petroleum ether and methylene chloride.
In a preferred embodiment of the invention, in step 2, the molar ratio of cholesterol formamidophenylacetonitrile to intermediate is from 1:1 to 1:1.3; cholesterol formamidophenylacetonitrile: sodium methoxide: the chromatographic ethanol is 3mmol:0.3-0.6mmol:30-50ml.
In a preferred embodiment of the invention, in step 2, the stirring reaction time is from 10 to 12 hours.
In a preferred embodiment of the present invention, in step 2, the temperature in the refrigerator is-10-0 ℃ and the time to put into the refrigerator is 2-3 hours.
In a preferred embodiment of the invention, in step 2, the volume molar ratio of ethanol to cholesterol formamidophenylacetonitrile used for each leaching is 2:1, and the leaching times are 3-6 times.
In a preferred embodiment of the present invention, a red to near infrared high luminous electrochromic material prepared by the above method is applied to a pressure detection material.
The principle and the beneficial effects of the invention are as follows: the static pressure electrochromic material provided by the invention has the characteristics of obvious color change (red changes into near infrared) and good sensitivity to external stimulus, and can be used for pressure sensing elements and optical recording by applying static pressure to the material to change the color of the material in a ratio.
Molecules form unique dimer stacks when aggregated, while unconjugated cholesterol can inhibit strong pi-pi interactions between molecules during close-packing.
Compared with the prior art, most of near infrared fluorescent molecules have low fluorescence efficiency, the synthesis is complex, the near infrared fluorescent molecules have high fluorescence efficiency (44.3%), 157nm spectrum red shift is generated, the synthesis is simple, and the application potential of the material in the field of pressure detection is greatly enhanced.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The foregoing and/or additional aspects and advantages of the invention will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
FIG. 1 is a fluorescence spectrum diagram of static pressure-induced ratio discoloration of near infrared benzothiadiazole cholesterol formamidophenone acetonitrile under pressure of 0atm-2.0 GPa;
FIG. 2 is a fluorescence spectrum of near infrared benzothiadiazole cholesterol formamidophene acetonitrile fluorescent dye static pressure ratio discoloration under pressure of 2.6-7 GPa;
FIG. 3 is a graph of static pressure versus spectrum for near infrared benzothiadiazole cholesterol formamidophene acetonitrile fluorescent dyes according to the invention.
FIG. 4 is a unique dimer stack of molecular formations.
Detailed Description
Embodiments of the present invention are described in detail below, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to like or similar elements or elements having like or similar functions throughout. The embodiments described below by referring to the drawings are illustrative only and are not to be construed as limiting the invention.
In the description of the present invention, it should be understood that the terms "longitudinal," "transverse," "vertical," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," and the like indicate or are based on the orientation or positional relationship shown in the drawings, merely to facilitate description of the invention and to simplify the description, and do not indicate or imply that the devices or elements referred to must have a particular orientation, be configured and operated in a particular orientation, and thus should not be construed as limiting the invention.
In the description of the present invention, unless otherwise specified and defined, it should be noted that the terms "mounted," "connected," and "coupled" are to be construed broadly, and may be, for example, mechanical or electrical, or may be in communication with each other between two elements, directly or indirectly through intermediaries, as would be understood by those skilled in the art, in view of the specific meaning of the terms described above.
The application provides a preparation method of a red to near infrared high luminous intensity electrochromic material, which comprises the following steps:
step 1, synthesizing an intermediate (II) 7-triphenylamine-4-aldehyde benzo [ c ] [1,2,5] thiadiazole:
the synthetic route is as follows:
the specific operation is as follows: weighing 7-bromo-4-aldehyde benzo [ c ] [1,2,5] thiadiazole, triphenylamine boric acid, tetra-triphenylphosphorus palladium and sodium carbonate, preparing sodium carbonate into sodium carbonate aqueous solution, and dissolving the raw materials into chromatographic toluene and tetrahydrofuran, wherein the molar ratio of 7-bromo-4-aldehyde benzo [ c ] [1,2,5] thiadiazole (III) to triphenylamine boric acid (IV) is 1:1-1:1.5; 7-bromo-4-aldehyde benzo [ c ] [1,2,5] thiadiazole: sodium carbonate: chromatographic toluene: chromatographic tetrahydrofuran is 10mmol:0.8-1.2mmol:50-60ml:30-40ml; under the protection of nitrogen atmosphere, refluxing and stirring for 12-24h, confirming the reaction progress through a spot plate when a large amount of red solid particles are precipitated, and stopping the reaction when the reaction is confirmed to be basically completed; the reaction solution was then extracted, filtered, separated by silica gel column chromatography using petroleum ether: dichloromethane = 2:1 leaching, and performing reduced pressure rotary evaporation to obtain red powder, namely a product intermediate (II);
step 2, synthesizing a target product (I):
the synthetic route is as follows:
the specific operation is as follows: weighing an intermediate (II), cholesterol formamidophenylacetonitrile (V) and sodium methoxide, and dissolving the intermediate (II), wherein the molar ratio of the cholesterol formamidophenylacetonitrile (V) to the intermediate (II) is 1:1-1:1.3; cholesterol formamidophenylacetonitrile (v): sodium methoxide: the chromatographic ethanol is 3mmol:0.3-0.6mmol:30-50ml. Stirring and reacting for 8-12h at 60 ℃ under the protection of nitrogen atmosphere, and stopping the reaction when a large amount of solid particles are separated out; then the reaction system is put into a refrigerator with the temperature of minus 20 ℃ to 0 ℃ for 8 hours to 10 hours, then the filter cake is filtered, the filter cake is leached with ethanol for 3 to 6 times, the volume mole ratio (L/mol) of the ethanol for each leaching and the cholesterol formamidophenylacetonitrile is 2:1, and red powder is obtained after drying, namely the target product benzothiadiazole cholesterol formamidophenylacetonitrile derivative (I). Wherein the molecular weight of (I) is 933.5g/mol; (II) molecular weight 407g/mol; (V) molecular weight 544g/mol;
the feeding ratio of the substances (II) and (V) is controlled to be 1:1 or (II) is slightly excessive, but not more than 1:1.3; the control range of the catalyst sodium methoxide is as follows: cholesterol formamidophenylacetonitrile (v): sodium methoxide=1 mmol:0.1-0.2mmol. A plurality of near infrared fluorescent molecules are reported before, the molecules generally have low fluorescence quantum efficiency, and the problems of complex synthesis exist, and the target molecules in the invention have high fluorescence quantum efficiency and simple synthesis, so that the huge application potential as a pressure sensing system is greatly increased.
The experimental mode is as follows:
experimental mode 1
Step 1, synthesizing an intermediate (II): 1.3g (6 mmol) of 7-bromo-4-aldehyde benzo [ c ] [1,2,5] thiadiazole (III), 1.8g (6.2 mmol) of triphenylamine boric acid (IV), 0.25g (0.22 mmol) of tetraphenylphosphine palladium and a sodium carbonate solution (3 mol/L) are weighed and dissolved in chromatographic toluene (50 ml) and tetrahydrofuran (30 ml), and the reaction is carried out under the protection of nitrogen atmosphere and reflux stirring at 80 ℃ for 12h until a large amount of red solid particles are precipitated, the reaction progress is determined, and the reaction is stopped. Dissolving all the crude products after the reaction is finished with dichloromethane, transferring, washing an organic phase with water, drying with anhydrous magnesium sulfate, removing a solvent by rotary evaporation, mixing the powdery products with the solvent removed with crude silica gel powder, loading the mixture into a column, and using dichloromethane and petroleum ether 1:2 as eluent to obtain the product intermediate (II) which is 1.68g in total, and the yield is 70%.
Step 2, 0.2g (0.55 mmol) of intermediate (II), 0.31g (0.55 mmol) of cholesterol formamidophenylacetonitrile (V) and 0.054g (1 mmol) of sodium methoxide were weighed and dissolved in 40ml of chromatographic ethanol. The reaction is stirred for 10 hours at 60 ℃ under the protection of nitrogen atmosphere, and the reaction is stopped when a large amount of solid particles are separated out. Then the ethanol solution of the product is put into a refrigerator at the temperature of minus 10 ℃ for 2 hours, and after solid precipitation is completed, the filtration is carried out, the filter cake obtained by filtration is leached by ethanol (20 mL multiplied by 3) for times, and the red powder is obtained after drying, wherein the total amount of the red powder is 0.30g, and the yield is 63.6%. Namely the target product benzothiadiazole cholesterol formamidophenylacetonitrile derivative (I).
Characterization data are as follows: 1 H NMR(400MHz,CDCl 3 )δ8.72(d,J＝7.6Hz,1H),8.49(s,1H),7.94(d,J＝8.8Hz,2H),7.84(d,J＝7.6Hz,1H),7.79(d,J＝8.8Hz,2H),7.54(d,J＝8.8Hz,2H),7.34(t,J＝8.4Hz,4H),7.23(m,6H),7.11(t,J＝7.6Hz,2H),6.77(s,1H),5.44(d,J＝4.8Hz,1H),4.67(m,1H),2.41(m,2H),1.61(m,12H),1.36(m,3H),1.16(m,8H),1.07(m,6H),0.94(d,J＝6.4Hz,3H),0.89(dd,J＝2.0Hz,J＝1.6Hz,6H),0.71(s,3H)；[M]+934.4986。
experimental mode 2
Step 1, synthesizing an intermediate (II): 2.11g (10 mmol) of 7-bromo-4-aldehyde benzo [ c ] [1,2,5] thiadiazole (III), 2.89g (10 mmol) of triphenylamine boric acid (IV), 0.25g (0.22 mmol) of tetraphenylphosphine palladium and 3mol/L of sodium carbonate solution (3 mol/L) are weighed and dissolved in chromatographic toluene (50 ml) and tetrahydrofuran (30 ml), and the reaction is carried out under the protection of nitrogen atmosphere and reflux stirring at 100 ℃ for 20h until a large amount of red solid particles are precipitated, the reaction progress is determined, and the reaction is stopped. Dissolving all the crude products after the reaction is finished with dichloromethane, transferring, washing an organic phase with water, drying with anhydrous magnesium sulfate, removing a solvent by rotary evaporation, mixing the powdery products with the solvent removed with crude silica gel powder, loading the mixture into a column, and using dichloromethane and petroleum ether 1:2 as eluent to obtain 3.2g of intermediate (II) with yield of 78.6%.
Step 2, 0.795g (1.95 mmol) of intermediate (II), 0.816g (1.5 mmol) of cholesterol formamidophenylacetonitrile (V) and 0.008g (0.15 mmol) of sodium methoxide were weighed and dissolved in 50ml of chromatographic ethanol. The reaction is stirred for 10 hours at 60 ℃ under the protection of nitrogen atmosphere, and the reaction is stopped when a large amount of solid particles are separated out. Then the resultant ethanol solution is put into a refrigerator at 0 ℃ for 3 hours, and after solid precipitation is completed, the filtration is carried out, the filter cake obtained by filtration is leached by ethanol (20 mL multiplied by 5) for times, and after drying, 1.1g of red powder is obtained, and the yield is 89.1%. Namely the target product benzothiadiazole cholesterol formamidophenylacetonitrile derivative (I).
Experimental mode 3
Step 1, synthesizing an intermediate (II): 1.06g (5 mmol) of 7-bromo-4-aldehyde benzo [ c ] [1,2,5] thiadiazole (III), 1.70g (7.5 mmol) of triphenylamine boric acid (IV), 0.25g (0.22 mmol) of tetraphenylphosphine palladium and sodium carbonate solution (3 mol/L) are weighed and dissolved in chromatographic toluene (60 ml) and tetrahydrofuran (40 ml), and the reaction is carried out under the protection of nitrogen atmosphere and reflux stirring at 90 ℃ for 20h until a large amount of red solid particles are precipitated, the reaction progress is determined, and the reaction is stopped. Dissolving all the crude products after the reaction is finished with dichloromethane, transferring, washing an organic phase with water, drying with anhydrous magnesium sulfate, removing a solvent by rotary evaporation, mixing the powdery products with the solvent removed with crude silica gel powder, loading the mixture into a column, and using dichloromethane and petroleum ether 1:2 as eluent to obtain the product intermediate (II) which is 1.65g and has a yield of 80.5%.
Step 2, 0.619g (1.52 mmol) of intermediate (II), 0.4265g (1.5 mmol) of cholesterol formamidophenylacetonitrile (V) and 0.016g (0.3 mmol) of sodium methoxide were weighed and dissolved in 40ml of chromatographic ethanol. The reaction was stirred at 60℃for 11h under nitrogen atmosphere and terminated when a large amount of solid particles had been precipitated. Then the ethanol solution of the product is put into a refrigerator with the temperature of minus 20 ℃ for 10 hours for cooling precipitation, and after solid precipitation is completed, the filtration is carried out, the filter cake obtained by filtration is leached by ethanol (20 mL multiplied by 4) for times, and the red powder is obtained after drying, wherein the total amount of the red powder is 1.02g, and the yield is 73 percent. Namely the target product benzothiadiazole cholesterol formamidophenylacetonitrile derivative (I).
Experimental mode 4
Step 1, synthesizing an intermediate (II): 2.11g (10 mmol) of 7-bromo-4-aldehyde benzo [ c ] [1,2,5] thiadiazole (III), 2.92g (10.1 mmol) of triphenylamine boric acid (IV), 0.25g (0.22 mmol) of tetraphenylphosphine palladium and a sodium carbonate solution (3 mol/L) are weighed and dissolved in chromatographic toluene (55 ml) and tetrahydrofuran (40 ml), and the reaction is carried out under the protection of nitrogen atmosphere and reflux stirring for 24h at 95 ℃ until a large amount of red solid particles are precipitated, the reaction progress is determined, and the reaction is stopped. Dissolving all the crude products after the reaction is finished with dichloromethane, transferring, washing an organic phase with water, drying with anhydrous magnesium sulfate, removing a solvent by rotary evaporation, mixing the powdery products with the solvent removed with crude silica gel powder, loading the mixture into a column, and using dichloromethane and petroleum ether 1:2 as eluent to obtain 3.4g of intermediate (II) with a yield of 76%.
Step 2, 0.619g (1.52 mmol) of intermediate (II), 0.816g (1.5 mmol) of cholesterol formamidophenylacetonitrile (V) and 0.054g (1 mmol) of sodium methoxide were weighed and dissolved in 30ml of chromatographic ethanol. The reaction is stirred for 12 hours at 60 ℃ under the protection of nitrogen atmosphere, and the reaction is stopped when a large amount of solid particles are separated out. Then the ethanol solution of the product is put into a refrigerator at the temperature of minus 10 ℃ for 10 hours, and is filtered after the solid is completely precipitated, the filter cake obtained by filtering is leached by ethanol (20 mL multiplied by 6) for times, and the red powder is obtained after drying, wherein the total amount of the red powder is 0.954g, and the yield is 68.0%. Namely the target product benzothiadiazole cholesterol formamidophenylacetonitrile derivative (I).
The target product benzothiadiazole cholesterol formamidophenylacetonitrile derivative (I) obtained in the above experimental modes 1 to 4 is shown in fig. 4, molecules form unique dimer stacks, red flaky crystals are obtained in a mixed solution of n-hexane and tetrahydrofuran by a solvent volatilization method, and the emission spectra under different pressures are explored, so that the relations between the fluorescence emission spectrum intensity and the wavelength and the static pressure are approximately clarified, and the relations are shown in fig. 1 and 2: the crystal can emit red to near infrared fluorescence, the fluorescence intensity is continuously reduced along with the increase of pressure, and the color of the fluorescence is gradually changed from red to near infrared. This phenomenon suggests that this material can be used in the field of pressure sensors or in the field of information storage. In addition, the spectrogram is processed to obtain a luminous peak position, and linear fitting is performed to obtain a static pressure and fluorescence emission spectrum peak position relation graph, as shown in fig. 3: in the process of gradually increasing static pressure, the luminescence of the red crystal gradually moves in red, the luminescence position and the static pressure of the red crystal show a certain linear relation, the relation between the pressure and the spectrum is 22.1nm/GPa, the wavelength is changed by 157nm, and the material can be used for pressure sensing elements.
In summary, the static pressure electrochromic material provided by the invention has the characteristics of obvious color change (as shown in fig. 3, at 1atm-7Gpa, with the increase of pressure, the wavelength is red shifted from 650nm to 806nm, the red shift is 156nm, the red is changed into near infrared, and thus the color change is obvious), good sensitivity to external stimulus (as can be seen from the spectrograms of fig. 1 and 2, with the increase of pressure, the fluorescence intensity is obviously reduced), and the material can be used for pressure sensing elements and optical recording by applying static pressure to the material to change the color ratio.
Most of near infrared fluorescent molecules have low fluorescence efficiency, the synthesis is complex, the near infrared fluorescent molecules have high fluorescence efficiency (44.3 percent), the synthesis is simple, and the huge application potential as a pressure sensing system is greatly increased
In the description of the present specification, reference to the terms "preferred implementation," "one embodiment," "some embodiments," "example," "a particular example" or "some examples" and the like means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
While embodiments of the present invention have been shown and described, it will be understood by those of ordinary skill in the art that: many changes, modifications, substitutions and variations may be made to the embodiments without departing from the spirit and principles of the invention, the scope of which is defined by the claims and their equivalents.
Claims (10)
1. A method for preparing a red to near infrared high luminous intensity electrochromic material, which is characterized by comprising the following steps: step 1, synthesizing an intermediate 7-triphenylamine-4-aldehyde benzo [ c ] [1,2,5] thiadiazole, wherein the structural formula of the 7-triphenylamine-4-aldehyde benzo [ c ] [1,2,5] thiadiazole is as follows:
weighing 7-bromo-4-aldehyde benzo [ c ] [1,2,5] thiadiazole, triphenylamine boric acid, tetra-triphenylphosphonium palladium and sodium carbonate, preparing sodium carbonate into sodium carbonate solution, and dissolving the raw materials into chromatographic toluene and tetrahydrofuran; under the protection of nitrogen atmosphere, refluxing and stirring for reaction, confirming the reaction progress through a spot plate when a large amount of red solid particles are precipitated, and stopping the reaction if the reaction is complete; then extracting, filtering, separating by column chromatography and rotary steaming to obtain red powder, namely the 7-triphenylamine-4-aldehyde benzo [ c ] [1,2,5] thiadiazole;
step 2, synthesizing a target product:
dissolving the intermediate product, cholesterol formamidophenylacetonitrile and sodium methoxide in chromatographic ethanol; stirring to react at 60 ℃ under the protection of nitrogen atmosphere, and stopping the reaction when a large amount of solid particles are separated out; then placing the chromatographic ethanol solution of the product into a refrigerator for cooling and separating out, filtering after solid precipitation is completed, leaching a filter cake obtained by filtering with ethanol for 3 times, and drying to obtain red powder, namely a target product, wherein the target product is a near infrared region color-changing dye benzothiadiazole cholesterol formamidophenylacetonitrile derivative; the structural formula of the benzothiadiazole cholesterol formamidophenylacetonitrile derivative is as follows:
wherein: the structural formula of the cholesterol formamidophenylacetonitrile is as follows:
2. the method for preparing a red to near infrared high luminous intensity electrochromic material according to claim 1, wherein the molar ratio of 7-bromo-4-aldehyde benzo [ c ] [1,2,5] thiadiazole to triphenylamine boric acid is 1:1-1:1.5; 7-bromo-4-aldehyde benzo [ c ] [1,2,5] thiadiazole: sodium carbonate: toluene: the dosage ratio of tetrahydrofuran is as follows: 10mmol, 0.8-1.2mmol, 50-60ml, 30-40ml, wherein the concentration of the sodium carbonate solution is 3mol/L.
3. The method for preparing a red to near infrared high luminous intensity electrochromic material according to claim 2, wherein in the step 1, the reflux stirring reaction time is 12-24h, and the reaction temperature is 80-100 ℃.
4. The method for preparing a red to near infrared high luminous intensity electrochromic material according to claim 3, wherein the extract is methylene chloride, and the eluent separated by column chromatography is petroleum ether and methylene chloride.
5. The method for preparing a red to near infrared high luminous intensity electrochromic material according to claim 4, wherein in the step 2, the molar ratio of cholesterol formamidophenylacetonitrile to intermediate product is 1:1-1:1.3; cholesterol formamidophenylacetonitrile: sodium methoxide: the chromatographic ethanol is 3mmol:0.3-0.6mmol:30-50ml.
6. The method for preparing a red to near infrared high luminous intensity electrochromic material according to claim 5, wherein in the step 2, the stirring reaction time is 10-12h.
7. The method for preparing a red to near infrared high luminous intensity electrochromic material according to claim 6, wherein in the step 2, the temperature in the refrigerator is-10-0 ℃ and the time for putting the material into the refrigerator is 2-3h.
8. The method for preparing a red to near infrared high luminous intensity electrochromic material according to claim 7, wherein in the step 2, the volume mole ratio of ethanol to cholesterol formamidophenylacetonitrile for each leaching is 2:1, and the leaching times are 3-6 times.
9. A C prepared by the process of any one of claims 1-8 61 H 67 N 5 O 2 S, the structural formula is as follows:
10. a red to near infrared high-luminescence electrochromic material prepared by the method of any one of claims 1 to 8 for use in a pressure detection material.
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